Cosmetic compositions containing hydrophobically modified nonionic polymer and unsaturated quaternary ammonium surfactant

ABSTRACT

Disclosed is a vehicle system having a thickening system which comprises a nonionic long-chain alkylated water-soluble polymer and a specific cationic quaternary ammonium surfactant component dispersed in a compatible solvent. The quaternary surfactant component has an iodine value of at least about 15. The quaternary surfactant component is characterized by having a sufficient level of unsaturated C 14  -C 22  alkyl or C 14  -C 22  alkyl amido C 2  -C 6  alkylene radicals such that the average iodine value is at least about 15. These vehicle systems are useful in cosmetic compositions which are used to deliver an active component to the hair or skin. The vehicle systems are particularly useful in hair care compositions, especially rinse-off hair conditioning and styling compositions. In a particular rinse-off hair styling and conditioning composition hereof, the composition contains a vehicle system, as described above, and additionally contains a hair setting agent, a distributing aid, and a mono-long chain, tri-short chain quaternary ammonium surfactant.

This is a division of application Ser. No. 08/113,454, filed on Aug. 27,1993, which is a continuation-in-part of application Ser. No.08/111,762, filed on Aug. 25, 1993, abandoned which is a continuation ofapplication Ser. No. 07/776,960, filed on Oct. 15, 1991, abandoned whichis a continuation-in-part of application Ser. No. 07/671,576, filed onMar. 19, 1991 abandoned.

TECHNICAL FIELD

The present invention relates to novel vehicle systems, and cosmeticcompositions formulated therewith, based on nonionic long chainalkylated water-soluble polymer derivatives and unsaturated quaternaryammonium surfactants in a compatible diluent. A particularly usefulapplication of the present invention is in hair care compositions,especially rinse-off hair conditioning and/or styling compositions.

BACKGROUND OF THE INVENTION

Typical hair conditioning products have a particular thick rheology thatis desirable for such products. These products are based on thecombination of a surfactant, which is generally a quaternary ammoniumcompound, and a fatty alcohol. This combination results in a gel-networkstructure which provides the composition with a thick rheology. However,while such compositions deliver conditioning benefits to the hair, suchcompositions also deposit on hair making hair look and feel dirty.

Alternative thickening systems have been used in hair care compositions,but none have been found to date which provide this same desirablerheology. Though hair care products thickened with polymer thickenerscan be made to have a thick rheology, these products generally arecharacterized by an undesirable "slimy" feel and do not hold theirpoured shape.

Nonionic water-soluble cellulose ethers are employed in a variety ofapplications, including hair care compositions. Widely used,commercially-available nonionic cellulose ethers include methylcellulose, hydroxy propyl methyl cellulose, hydroxyethyl cellulose,hydroxypropyl cellulose and ethyl hydroxyethyl cellulose.

Better thickening efficiency is realized with higher molecular weightcellulose ethers. However, production of such materials is difficult andexpensive. Though crosslinking of these polymers is an alternative meansto achieve high viscosity solutions, good crosslinking techniques arenot known. Of course, high concentrations of polymers will also providehigh viscosity but such an approach is inefficient and impractical,particularly due to the high expense involved. Furthermore, use ofhighly crosslinked polymers or high levels of polymeric thickeners mayresult in a vehicle system that is too elastic for the present uses.

Alternative water-soluble polymeric thickeners sometimes used to thickenhair care compositions are natural polysaccharides such as guar gum,xanthan gum and locust bean gum.

A number of references teach the use of nonionic cellulose ethers andwater-soluble gums for thickening hair care compositions. See forexample, U.S. Pat. No. 4,557,928, Glover, issued Dec. 10, 1985, teachinga hair conditioner comprising a suspension system which consists of oneof glucan gum, guar gum, and hydroxyethylcellulose; and U.S. Pat. No.4,581,230, Grollier et al., issued Apr. 8, 1986, which teaches cosmeticcompositions for treating hair which comprise as thickening agentshydroxyethylcellulose, or water-soluble vegetable thickening agents,such as guar gum. Japanese Patent Publication 61-053211, published Mar.7, 1986, discloses a hair colorant containing an aromatic alcohol,xanthan gum, and hydroxyethylcellulose.

Certain cellulose ethers have been disclosed in U.S. Pat. No. 4,228,277,Landoll, issued Oct. 14, 1980, which are relatively low molecular weightbut which are capable of producing highly viscous aqueous solutions inpractical concentrations. These materials are nonionic cellulose ethershaving a sufficient degree of nonionic substitution selected from thegroup consisting of methyl, hydroxyethyl, and hydroxypropyl to causethem to be water-soluble and which are further substituted with ahydrocarbon radical having from about 10 to 24 carbon atoms in an amountbetween about 0.2 weight percent and the amount which renders saidcellulose ether less than 1%, by weight, soluble in water. The celluloseether to be modified is preferably one of low to medium molecularweight; i.e., less than about 800,000 and preferably between about20,000 and 700,000 (about 75 to 2500 D.P.).

These modified cellulose ethers have been disclosed for use in a varietyof composition types. Landoll ('277) teaches the use of these materialsin shampoo formulations. Hercules trade literature teaches the use ofthese materials in shampoos, liquid soaps, and lotions. U.S. Pat. No.4,683,004, Goddard, issued Jul. 28, 1987, discloses the use of thesematerials in mousse compositions for the hair. U.S. Pat. No. 4,485,089,Leipold, issued Nov. 27, 1984, teaches dentifrice compositionscontaining these materials.

These materials have now been found to provide a rheology very much likethe desirable gel-network structure of typical hair conditioners(without the slimy feel associated with most polymeric thickeners), whenthey are combined with surfactants at certain critical levels. Suchcompositions are disclosed in U.S. Ser. Nos. 07/551,118, 07/551,119, and07/551,120, all filed Jul. 16, 1990, by Bolich, Norton, and Russell.

Still, it remains desirable to provide further improved vehicle systemsfor use for cosmetic compositions. In particular, it is desirable toimprove perceived spreadability of the compositions upon application bythe user to the hair or skin. It is also desirable to provide improvedwet feel of the hair on skin treated with such cosmetic compositions.

Hence, it is an object of the present invention to provide a vehiclesystem for a hair care and other cosmetic composition which provides agel-network-like structure to the composition not based on a typicalquaternary ammonium compound/fatty alcohol gel-network thickeningsystem, which provides improved perceived spreadability upon applicationto the skin or hair and which provides improved wet feel of the hair orskin to the touch.

It is also an object of the present invention to provide a vehiclesystem, as described above, for a hair care and other cosmeticcompositions which allows for dispersion of a wide variety of activehair or skin care components therein while providing improved wet feeland perceived spreadability relative to such compositions with priordisclosed vehicle systems.

In a particular aspect of this patent, it is an object to provide hairstyling/conditioning compositions having excellent wet hair feel. Suchcompositions contain hair setting agents which typically should beaccompanied by a distributing aid to facilitate spreading of the hairsetting agent upon application to hair. The use of distributing aids,such as xanthan gum, unfortunately can negatively impact wet hair feel.Thus it is another object of this invention to provide a hair stylingand conditioning composition containing a distributing aid for the hairsetting agent that has excellent wet hair feel characteristics.

These and other objects will become readily apparent from the detaileddescription which follows.

SUMMARY OF THE INVENTION

The present invention relates to vehicle systems for use in cosmeticcompositions which are polymer-based but which provide a rheology to thecosmetic compositions which mimics gel-network systems. These vehiclesystems comprise a two component thickening system in a compatiblediluent, wherein the primary thickener component is hydrophobicallymodified, nonionic, long chain alkoxylated polymer that is soluble inthe diluent and the second thickener component is selected fromquaternary ammonium surfactants having the formula, in salt form:##STR1## wherein X is a salt-forming anion, a is the ionic charge of X,the quaternary ammonium radicals R₁, R₂, R₃, and R₄ independently are C₁-C₂₂ alkyl, C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, or benzyl, and fromtwo to three of said quaternary ammonium radicals, preferably two, areC₁₄ -C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene (preferably C₂-C₃ alkylene), preferably C₁₆ -C₂₂ alkyl, more preferably C₁₆ -C₁₈alkyl, or mixtures thereof, no more than two of said radicals are eitherC₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene or a combination of C₁₄ -C₂₂ alkyland C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, from one to two of saidquaternary ammonium radicals, preferably two, are C₁ -C₆ alkyl,preferably C₁ -C₃ alkyl, more preferably methyl, and no more than one ofsaid radicals is benzyl; or ##STR2## wherein X and a are as definedabove, the radicals R₁, R₂, and R₃ independently are C₁ -C₂₂ alkyl orbenzyl, preferably C₁ -C₂₂ alkyl, and two or three of said radicals areC₁₄ -C₂₂ alkyls, preferably C₁₆ -C₂₂ alkyl, or C₁₄ -C₂₂ alkyl amido C₂-C₆ alkylene (preferably C₂ -C₃ alkylene), or a mixture thereof, zero orone of said radicals are C₁ -C₆ alkyl, preferably C₁ -C₃ alkyl, morepreferably methyl, zero or one of said radicals is benzyl; or a mixtureof Formula I and II surfactants; wherein the quaternary ammoniumsurfactant component of the above description has a sufficient levelunsaturation in the C₁₄ -C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆alkylene radicals, or mixtures thereof, such that average iodine valueof said component is at least about 15.

More specific embodiments of the cosmetic compositions of the presentinvention comprise:

(a) from about 80% to about 100%, preferably from about 80% to about99.9%, of a vehicle system which comprises:

(A) from about 0.1% to about 10% by weight of the cosmetic compositionof a hydrophobically modified nonionic water-soluble polymer whichcomprises a water-soluble polymer backbone and hydrophobic groupsselected from the group consisting of C₈ -C₂₂ alkyl, aryl alkyl, alkylaryl groups and mixtures thereof; wherein the ratio of hydrophilicportion to hydrophobic portion of the polymer is from about 10:1 toabout 1000:1; preferably the hydrophobically modified nonionicwater-soluble polymer comprises a nonionic cellulose ether having asufficient degree of nonionic substitution selected from the groupconsisting of methyl, hydroxyethyl, and hydroxypropyl to cause it to bewater-soluble and being further substituted with a long chain alkylradical having 10 to 24 carbon atoms in an amount between about 0.2weight percent and the amount which renders said cellulose ether lessthan 0.2, preferably less than 1%, by weight soluble in water;

(B) from about 0.02% to about 5.0% by weight of the cosmetic compositionof unsaturated quaternary ammonium surfactant as described above; and

(C) from about 65% to about 99% by weight of the cosmetic composition ofa compatible diluent, said nonionic water-soluble polymer being solublein said diluent; and

(b) from 0 to about 20%, preferably from about 0.1% to about 20%, of anadditional active cosmetic component; wherein compositions comprisingsaid vehicle system comprise no more than about 10% preferably no morethan about 0.5%, of water-soluble surfactant materials (at 25° C.).

The unsaturated cationic quaternary ammonium surfactant as set forthabove, can provide improved perceived spreading and improved wet feel ofthe hair or skin upon application by the user. These vehicle systems areparticularly useful in hair care compositions especially rinse-off hairconditioners and styling/conditioners.

In another aspect of this invention, hair styling and conditioningcompositions suitable for rinse-off application are provided with yetfurther improved wet hair feel. These compositions contain a twocomponent thickening system in a compatible solvent as described aboveand a hair setting agent dispersed in the composition, a distributingaid for the hair setting agent, and additionally comprise as anessential ingredient a mono-long chain, tri-short chain cationicammonium quaternary surfactant, or a mixture thereof, wherein the longchain is selected from C₁₄ -C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆alkylene and the short chains independently are selected from the groupconsisting of C₁ -C₆ alkyl and benzyl, with the number of benzylradicals per molecule being zero or 1.

More specific embodiments of these hair styling and conditioningcompositions comprise:

(a) from about 80% to about 99.5% of a vehicle system comprising:

(A) from about 0.1% to about 10.0% by weight of the cosmetic compositionof a hydrophobically modified nonionic water-soluble polymer whichcomprises a water-soluble polymer backbone and hydrophobic groupsselected from the group consisting of C₈ -C₂₂ alkyl, aryl alkyl, alkylaryl groups and mixtures thereof; wherein the ratio of the hydrophilicportion to the hydrophobic portion of the polymer is from about 10:1 toabout 1000:1; and

(B) from about 0.02% to about 10.0% by weight of the cosmeticcomposition of a unsaturated quaternary ammonium surfactant component ofthe formula: ##STR3## wherein X is a salt-forming anion, a is the ioniccharge of X, the quaternary ammonium radicals R₁, R₂, R₃, and R₄independently are C₁ -C₂₂ alkyl, C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene,or benzyl, and from two to three of said quaternary ammonium radicals,are C₁₄ -C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene or mixturesthereof, no more than two of said radicals being C₁₄ -C₂₂ alkyl amido C₂-C₆ alkylene or a combination of C₁₄ -C₂₂ alkyl and C₁₄ -C₂₂ alkyl amidoC₂ -C₆ alkylene, from one to two of said quaternary ammonium radicalsare C₁ -C₆ alkyls, and no more than one of said radicals is benzyl; or##STR4## wherein X is a salt-forming anion, a is the ionic charge of X,radicals R₁, R₂, and R₃ independently are C₁ -C₂₂ alkyl or benzyl, andtwo or three of said radicals are C₁₄ -C₂₂ alkyl, or C₁₄ -C₂₂ alkylamido C₂ C₆ alkylene or a mixture thereof, zero or one of said radicalsare C₁ -C₆ alkyl, zero or one of said radicals is benzyl, or a mixtureof Formula I and II surfactants; wherein said the quaternary ammoniumsurfactant component has a sufficient level of unsaturation in the C₁₄-C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene radicals, or mixturethereof, such that average iodine value of said component is at least15; and

(C) from about 65% to about 99% by weight of the cosmetic composition ofa compatible diluent; and

(b) from 0.05% to about 10%, by weight of the composition, of a hairsetting agent;

(c) from about 0.01% to about 5% of a distributing aid; and

(d) from about 0.05% to about 1.0%, by weight of the composition, of amono-long chain, tri-short chain quaternary ammonium surfactant, or amixture thereof of the formula: ##STR5## wherein X is a salt forminganion, a is the ionic charge of X, the quaternary ammonium radical R₁ isC₁₄ -C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, and quaternaryammonium radicals R₂, R₃, and R₄ independently are C₁ -C₆ alkyl orbenzyl, wherein zero or one of said R₂, R₃, and R₄ radicals is benzyl;

wherein said composition comprises no more than about 1.0% ofwater-soluble surfactants.

The compositions hereof comprise or, alternately, can consistessentially of or consist of the essential ingredients, as well as theoptional ingredients, described herein.

DETAILED DESCRIPTION OF THE INVENTION

The essential as well as various optional components of the presentcompositions are described below. All solubilities are determined at 25°C., unless otherwise indicated. All percentages and ratios are by weightunless otherwise indicated. All percentages are by weight of the totalcomposition, unless otherwise indicated.

HYDROPHOBICALLY MODIFIED WATER SOLUBLE POLYMER

The vehicle systems of the present invention contain, as an essentialthickener component, a water soluble polymer. This thickening materialis a hydrophobically modified nonionic water-soluble polymer. By"hydrophobically modified nonionic water-soluble polymer" is meant anonionic water-soluble polymer which has been modified by thesubstitution with a sufficient amount of hydrophobic groups to make thepolymer less soluble in water. Hence, the polymer backbone can beessentially any water-soluble polymer. For the compositions hereof, theunmodified polymer backbone should be sufficiently soluble such thatforms a substantially clear solution when dissolved in water at a levelof 1%, by weight of the solution, at 25° C. The hydrophobic groups canbe C₈ to C₂₂ alkyl, aryl alkyl, alkyl aryl groups and mixtures thereof.The degree of hydrophobic substitution on the polymer backbone should befrom about 0.10% to about 1.0%, by total weight of the polymer,preferably from about 0.4% to about 0.7%. More generally, the ratio ofhydrophilic portion to hydrophobic portion of the polymer is from about10:1 to about 1000:1.

A number of existing patents disclose nonionic polymer materials whichmeet the above requirements and which are useful in the presentinvention. U.S. Pat. No. 4,496,708, Dehm et al., issued Jan. 29, 1985,teaches water-soluble polyurethanes having hydrophilic polyetherbackbones and pendant monovalent hydrophobic groups to result in ahydrophilic/lipophilic balance of between about 14 and about 19.5. U.S.Pat. No. 4,426,485, Hoy et al., issued Jan. 17, 1984, discloses awater-soluble thermoplastic organic polymer having segments of bunchedmonovalent hydrophobic groups. U.S. Pat. No. 4,415,701, Bauer, issuedNov. 15, 1983, discloses copolymers containing a monoepoxide and adioxolane.

The most preferred hydrophobically modified water soluble polymericthickener materials for use in the present invention are disclosed inU.S. Pat. No. 4,228,277, Landoll, issued Oct. 14, 1980, which isincorporated herein by reference. The materials disclosed therein arethickeners comprising a nonionic long chain alkylated cellulose ether.

The cellulose ethers have a sufficient degree of nonionic substitutionselected from the group consisting of methyl, hydroxyethyl andhydroxypropyl to cause them to be water-soluble. The cellulose ethersare further substituted with a hydrocarbon radical having about 10 to 24carbon atoms in an amount between about 0.2 weight percent and theamount which renders said cellulose ether less than 0.2%, preferablyless than 1%, by weight, soluble in water. The cellulose ether to bemodified is preferably one of low to medium molecular weight, i.e., lessthan about 800,000 and preferably between about 20,000 and 700,000(about 75 to 2500 D.P.).

The Landoll patent teaches that any nonionic water-soluble celluloseether can be employed as the cellulose ether substrate. Thus, e.g.,hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose,hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, and methylhydroxyethyl cellulose can all be modified. The amount of nonionicsubstituent such as methyl, hydroxyethyl or hydroxypropyl is taught notto be critical so long as there is an amount sufficient to assure thatthe ether is water-soluble.

The preferred cellulose ether substrate is hydroxyethyl cellulose (HEC)of about 50,000 to 700,000 molecular weight. Hydroxyethyl cellulose ofthis molecular weight level is the most hydrophilic of the materialscontemplated. It can thus be modified to a greater extent than can otherwater-soluble cellulose ether substrates before insolubility isachieved. Accordingly, control of the modification process and controlof the properties of the modified product can be more precise with thissubstrate. Hydrophilicity of the most commonly used nonionic celluloseethers varies in the general direction:hydroxyethyl→hydroxypropyl→hydroxypropyl methyl→methyl.

The long chain alkyl modifier can be attached to the cellulose ethersubstrate via an ether, ester or urethane linkage. The ether linkage ispreferred.

Although the materials taught in Landoll are referred to as being "longchain alkyl group modified", it will be recognized that except in thecase where modification is effected with an alkyl halide, the modifieris not a simple long chain alkyl group. The group is actually analphahydroxyalkyl radical in the case of an epoxide, a urethane radicalin the case of an isocyanate, or an acyl radical in the case of an acidor acyl chloride. Nonetheless, the terminology "long chain alkyl group"is used since the size and effect of the hydrocarbon portion of themodifying molecule completely obscure any noticeable effect from theconnecting group. Properties are not significantly different from thoseof the product modified with the simple long chain alkyl group.

Methods for making these modified cellulose ethers are taught in Landoll('277) at column 2, lines 36-65.

These materials have been found to be particularly desirable for use inthe vehicle systems of the cosmetic compositions of the presentinvention. The materials are able to stabilize suspensions of dispersedphases, and when used with the additional components in the vehiclesystems of the present invention, they produce rheologically thickproducts which lack the slimy feel characteristic of most polymericthickeners.

One commercially available material which meets these requirements isNATROSOL PLUS Grade 330, a hydrophobically modifiedhydroxyethylcellulose available from Aqualon Company, Wilmington, Del.This material has a C₁₆ alkyl substitution of from about 0.4% to about0.8% by weight. The hydroxyethyl molar substitution for this material isfrom about 3.0 to about 3.7. The average molecular weight for thewater-soluble cellulose prior to modification is approximately 300,000.Another material of this type has a C₁₆ alkyl substitution of from about0.40% to about 0.95%, by weight. The hydroxyethyl molar substitution forthis material is from about 2.3 to about 3.3, and may be as high asabout 3.7. The average molecular weight for the water soluble celluloseprior to modification is approximately 700,000.

The hydrophobically modified water soluble polymer thickener componentis present in the cosmetic compositions of the present invention at fromabout 0.1% to about 10.0%, preferably from about 0.2% to about 5.0%.

UNSATURATED QUATERNARY AMMONIUM SURFACTANT

The present vehicle systems further comprise, as a second essentialcomponent, a second thickener which is an unsaturated water-insoluble,C₁₄ -C₂₂ alkyl-substituted quaternary ammonium surfactant. By"water-insoluble surfactant" is meant surfactant materials which do notform clear isotropic solutions when dissolved in water at greater than0.2 weight percent at 25° C. By "unsaturated" as applied to the C₁₄ -C₂₂alkyl substituted quaternary ammonium surfactant is meant quaternaryammonium surfactants having a sufficient amount of unsaturation suchthat it has an iodine value of at least about 15. Generally, the iodinevalue will be from about 20 to about 200. It should be understood thatthe iodine value is meant to describe the average level of unsaturationof the essential C₁₄ -C₂₂ alkyl substituted quaternary ammoniumsurfactant. "Alkyl" as used herein, includes unsaturated radicals aswell as saturated.

The essential C₁₄ -C₂₂ alkyl-substituted quaternary ammonium surfactantcomponent hereof constitutes materials of the formula, in salt form:##STR6## wherein X is a salt-forming anion, a is the ionic charge of X,the quaternary ammonium radicals R₁, R₂, R₃, and R₄ independently are C₁-C₂₂ alkyl, C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, or benzyl, and fromtwo to three of said quaternary ammonium radicals, preferably two, areC₁₄ -C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene (preferably C₂-C₃ alkylene), preferably C₁₄ -C₂₂ alkyl, more preferably C₁₆ -C₁₈alkyl, or mixtures thereof, no more than two of said radicals are eitherC₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene or a combination of C₁₄ -C₂₂ alkyland C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, from one to two of saidquaternary ammonium radicals, preferably two, are C₁ -C₆ alkyls,preferably C₁ -C₃ alkyl, more preferably methyl, and no more than one ofsaid radicals is benzyl; or ##STR7## wherein X and a are as definedabove, the radicals R₁, R₂, and R₃ independently are C₁ -C₂₂ alkyl orbenzyl, preferably C₁ -C₂₂ alkyl, and two or three of said radicals,preferably two, are C₁₄ -C₂₂ alkyl, preferably C₁₆ -C₂₂ alkyl, or C₁₄-C₂₂ alkyl amido C₂ -C₆ alkylene (preferably C₂ -C₃ alkylene), or amixture thereof, zero or one of said radicals are C₁ -C₆ alkyl,preferably C₁ -C₃ alkyl, more preferably methyl, zero or one of saidradicals is benzyl, or a mixture of Formula I and II surfactants;wherein the quaternary ammonium surfactant component of the abovedescription has a sufficient level unsaturation in the C₁₄ -C₂₂ alkyl orC₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene radicals, or mixtures thereof, suchthat average iodine value of said component is at least about 15.

The anion X can be any salt-forming anion suitable for use in cosmeticcompositions. Suitable anions include halogens (especially chloride andbromide), acetate, phosphate, nitrate, sulfate, and alkyl sulfate.Preferred anions generally are chloride, acetate, sulfate, and methylsulfate.

Examples of unsaturated quaternary ammonium surfactants hereof includethe salts of dimethyl di(unsaturated)tallow ammonium, dimethyl distearylammonium, dimethyl di(unsaturated)arachidyl ammonium, dioleyldimethylammonium, di-rapeseed alkyl dimethyl ammonium, diricinoleyldimethyl ammonium, and disoyadimonium, olealkonium.

Other examples include the salts of methyl-1-oleyl amido ethyl-2-oleylimidazolinium, dierucyl dimethyl ammonium, and methyl-1-soya amidoethyl-2-soya imidazolinium.

It will be recognized by those skilled in the art that unsaturatedquaternary ammonium surfactants, when purchased commercially, willnormally also contain saturated quaternary ammonium surfactants ofotherwise similar structure. An example of this is ADOGEN 470,commercially available from Sherex Chemical Company (Dublin, Ohio,U.S.A.), which contains a mixture of saturated and unsaturated ditallowdimethyl ammonium chloride. Compositions containing such materials areincluded within the scope of this invention as long as they contain theminimum level of surfactant defined herein having a level ofunsaturation of surfactant falling within Formula (I) and (II) issufficient such that the average iodine value is at least about 15.

This quaternary ammonium surfactant hereof is used at a level of fromabout 0.02% to about 10.0%, preferably from about 0.05% to about 3.0%,more preferably from about 0.05% to about 2.0%, by weight, of thecomposition.

Whereas the water insoluble unsaturated quaternary ammonium surfactantcomponent hereof is referred to as a thickener material, it should alsobe recognized that it can also act as a conditioner for the hair and/orskin.

DILUENT

A third essential component in the vehicle systems of the presentinvention is a diluent which is a solvent for the hydrophobicallymodified water-soluble polymer and is compatible with the othercomponents in the present compositions. Generally the diluent willcomprise water or a water-lower alkanol (e.g., C₂ -C₄ alcohols) mixture;preferably it will include at least about 25%, more preferably at leastabout 50%, even more preferably at least about 75%, by total weight ofthe diluent, of water. Rinse-off compositions, such as hair rinses,preferably utilize water as the diluent. The diluent is present in thecompositions of the present invention at a level of from about 65% toabout 99% by weight of the cosmetic composition.

The other vehicle components are dispersed or mixed in the diluent toprovide an optimum thick rheology to cosmetic compositions formulatedtherewith which mimics the gel-network rheology of typical hairconditioning compositions. This rheology is characterized by a shearstress of from 0 to about 50 pascal, over a shear rate range of 0.04sec⁻¹ to 25 sec⁻¹. The rheology is measured using a Bohlin Rheometer VORwith the following cone and plate set-up: cone has a 2.5 degree angle,plate is 30 mm in diameter, the gap between the truncated cone and plateis set at 70 μm, and the torque bar used is 20.148 g-cm. The sampleamount is 0.35 ml and the sample is syringed onto the center of theplate. The system used is as follows: there is no initial delay time,the strain delay time is 25 sec, the integration time is 5 sec, thesensitivity is set at 1×, the shear sweep is up, the shear range is fromabout 0.0405 sec⁻¹ to 25.53 sec⁻¹ (shear No.=11 to 39), and thetemperature is maintained constant between series at ambient temperature(20° C. to 25° C.).

ADDITIONAL THICHENER

The present vehicle systems can also comprise an additional thickeningcomponent, such as water-soluble polymeric materials other than thehydrophobically modified water soluble polymers described above.Examples of water-soluble polymers which may desirably be used as anadditional thickening component in the present vehicle systems, arehydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropylmethylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid,polyvinyl alcohol, polyvinyl pyrrolidone K-120, dextrans, for exampleDextran purified crude Grade 2P, available from D&O Chemicals,carboxymethyl cellulose, plant exudates such as acacia, ghatti, andtragacanth, seaweed extracts such as sodium alginate, propylene glycolalginate and sodium carrageenan, and UCARE JR-polymer (a cationicmodified hydroxyethyl cellulose available from Union Carbide). Preferredas the optional additional thickener for the present vehicle systems arenatural polysaccharide materials. Examples of such materials are guargum, locust bean gum, and xanthan gum. Also preferred as the additionalthickener in the present compositions is hydroxyethyl cellulose having amolecular weight of about 700,000. It is preferred that these polymermaterials not contain cellulose as this may interfere with obtainingoptimum viscosities.

The additional thickening component, if present in the cosmeticcompositions of the present invention, is preferably used at a level offrom about 0.3% to about 5.0%, preferably from about 0.4% to about 3.0%.

DISTRIBUTING AID

An additional component in the vehicle systems of the present inventionis a material which acts as a distributing aid for the composition. Sucha material helps to distribute the cosmetic composition onto the hair orskin avoiding localized deposition of the active component onto the hairor skin. Without such a component in a composition, some activecomponents in the composition would not be deposited and spread out asevenly, and hence, would not be quite as effective. In particular, adistributing aid is especially useful if ingredients that are tacky areincluded, such as hair setting polymers.

Distributing aid materials useful in the present invention are actuallya subclass of the class of materials that can be used as the optionalwater-soluble polymer additional thickener in the present invention.This subclass is defined as follows: water-soluble polymer materialshaving high molecular weight, i.e., greater than 1,000,000; and/orstrong ionic character. By strong ionic character is meant that thematerial conducts electricity at greater than 30 millivolts. This can bemeasured by evaluating conductance of a 1% solution of polymer in DRO(double reverse osmosis) water preserved with 0.03% Kathon CG(methylchloroisothiazolinone and methylisothiazolinone, a preservativeavailable from Rohm & Haas) using a calibrated Corning 130 pH meter. Theprobes used were as follows: the reference electrode is an Orion Model9001 single junction. The pH electrode is an Orion Model 9161,silver-silver chloride. The probes are set 3/8 of an inch apart. The pHmeter is set to millivolt readings. The absolute measurement is recordedafter 4 minutes immersion.

Examples of water soluble polymer materials which meet theserequirements and hence, can act as distributing aids in the presentcompositions include xanthan gum; Dextran purified crude Grade 2Pavailable from D&O chemicals; carboxymethyl celluloses; for example,CMC's 4H1F, 4M6F, 7HF, 7M8SF, 7LF, 9H4F, 9M8, 12M8P, 16M31, (allavailable from Aqualon); plant exudates such as acacia, ghatti andtragacanth; seaweed extracts such as sodium alginate, propylene glycolalginate, and sodium carrageenan; high molecular weight hydroxyethylcelluloses such as Natrosol 250H and Natrosol 250HHR (available fromAqualon); and pectin.

Because the class of materials which may act as distributing aids in thepresent invention is a subset of the optional water-soluble additionalthickener, the materials in this subclass may be used to provide bothbenefits to the composition. For example, xanthan gum is a water-solublenatural polysaccharide material which additionally has a high molecularweight. Hence, this material could be used by itself to provide bothadditional thickening benefits and distributing benefits. However, itmay be necessary to use such materials at slightly higher levels toprovide both benefits.

It is also possible to use two separate materials as the optionalwater-soluble polymer additional thickener and the distributing aid ofthe present invention. This would be done when the water-soluble polymeradditional thickener was not a high molecular weight material or ofstrong ionic character. Locust bean gum is such a material. Adistributing aid such as xanthan gum could be used with locust bean gumto provide the additional distributing benefits.

If a distributing aid is present in the cosmetic compositions of thepresent invention, it should be present at a level of from about 0.02%to about 2.5%, preferably from about 0.05% to about 1.0%, of thecosmetic composition. If the distributing aid is bifunctional, i.e.,acting as both the optional additional thickener and the distributingaid it should be present at a level of from about 0.2% to about 5% ofthe composition. Thus, in general, the distributing aid will be used ata level of about 0.02% to about 5%.

A distributing aid is particularly useful in hair care compositions ofthe present invention especially rinse-off hair conditioners. Thedistributing aid helps to spread some hair conditioning components,especially hair setting agents, evenly over the hair.

The present vehicle systems and cosmetic compositions formulatedtherewith should be substantially free of water-soluble surfactants.These materials are not compatible with the vehicle systems of thepresent composition. By "substantially free of water-solublesurfactants" is meant that the compositions comprise less than an amountof such surfactants that will destroy the present unique desirablerheology that is the object of the prevent invention. Generally, thiswill mean that the present compositions comprise no more than about 1%,preferably no more than about 0.5%, of such materials. Examples ofspecific water-soluble surfactant materials that can be particularlyharmful to the present vehicle systems are alkyl sulfates andethoxylated alkyl sulfates, such as ammonium lauryl sulfate; amphotericsurfactants which are derivatives of aliphatic secondary and tertiaryamines; nonionic surfactants produced by the condensation of alkyleneoxide groups with an organic hydrophilic compound, such as laureth-23(sold under the trademark Brij 35 by ICI Americas); and high alkylbetaines, sulfo betaines, amido betaines and amido sulfobetaines, suchas cetyl betaine.

The present vehicle systems and cosmetic compositions formulatedtherewith are also preferably substantially free of fatty alcoholmaterials, such as stearyl-, cetyl-, myristyl-, behenyl-, lauryl-, andoleyl alcohol. By "substantially free of fatty alcohol materials" ismeant that the compositions of the present invention comprise no morethan about 1% of these materials. These materials are commonly used invehicle systems for hair conditioner products. However, these materialstend to deposit on the hair and leave the hair feeling dirty after use.These materials are not required in the present vehicle systems, as theyare thickened with alternative materials which do not deposit on hair.

The present vehicle systems can be used in essentially any cosmeticproducts having a thick gel-network type rheology and which are used todeliver some active component onto the hair or skin. Such compositionswould include skin moisturizing lotions, sunscreen compositions, andskin cleansing compositions. However, cosmetic compositions mostdesirably used with the present vehicle systems are hair care products,especially rinse-off hair care products where some active hair carecomponent is to be deposited onto the hair but the vehicle carrying thatcomponent is desirably rinsed off of the hair with little or nodeposition of the vehicle material onto the hair.

Generally, the present vehicle systems will not be useful in typicalshampoo compositions since these compositions contain high levels ofwater-soluble surfactants, which as discussed supra, are incompatiblewith the present vehicle systems. However, the present vehicle systemsare useful in typical hair coloring compositions, hair tonic or gelcompositions, hair mousse compositions, and especially hair conditioningcompositions.

ACTIVE COSMETIC COMPONENT

The cosmetic compositions of the present invention generally willcomprise an additional active cosmetic component which provides somebenefit to the hair or skin. The term "additional active component" isused since the unsaturated quaternary ammonium surfactant componenthereof generally operates as a conditioner to hair or skin. Suchmaterials may include moisturizing agents, sunscreen agents, cleaningagents (that are compatible with the present vehicle systems), andespecially hair conditioning agents, hair styling agents, antidandruffagents, hair growth promoters, hair dyes and pigments, or perfumes.

A wide variety of conventional sunscreening agents are suitable for usein the cosmetic compositions of the present invention. Segarin, et al.,at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology,disclose numerous suitable agents. Specific suitable sunscreening agentsinclude, for example: p-aminobenzoic acid, its salts and itsderivatives; anthranilates; salicylates; cinnamic acid derivatives;dihydroxycinnamic acid derivatives; trihydroxycinnamic acid derivatives;hydrocarbons; dibenzalacetone and benzalacetophenone;naphtholsulfonates; dihydroxy-naphtholic acid and its salts; coumarinderivatives; diazoles; quinine salts; quinoline derivatives; hydroxy- ormethoxy-substituted benzophenones; uric and vilouric acids; tannic acidand its derivatives; hydroquinone; and benzophenones.

Of these, 2-ethylhexyl p-methoxycinnamate, 4,4'-t-butylmethoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyldimethylp-aminobenzoic acid, digalloyltrioleate,2,2-dihydroxy-4-methoxybenzophenone, ethyl-4-bis(hydroxypropyl)!-aminobenzoate,2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate,glyceryl p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate,methylanthranilate, p-dimethyl-aminobenzoic acid or aminobenzoate,2-ethylhexyl p-dimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonicacid 2-(p-dimethyl-aminophenyl)-5-sulfonicbenzoxazoic acid, and mixturesof these compounds are particularly useful.

Examples of antidandruff aids suitable for use with the vehicle systemsof the present invention include zinc pyrithione, sulphur, and seleniumsulfide. One example of a hair growth promoter suitable for use with thevehicle systems of the present invention is Minoxidil,(6-amino-1,2-dihydro-1-hydrpxy-2-imino-4-piperidino pyrimide) availablefrom Upjohn. Hair oxidizing (bleaching) agents, such as hydrogenperoxide, perborate and persulfate salts, and hair reducing agents suchas thioglycolates may also be used.

Additional Conditioners

Examples of conditioning materials suitable for use in the vehiclesystems of the present invention are volatile liquid hydrocarbons. Theseare particularly useful for use in hair treatments.

These materials preferably have a boiling point in the range of about99° C. to about 260° C. and have a solubility in water of less thanabout 0.1%. The hydrocarbons may be either straight or branched chainand may contain from about 10 to about 16, preferably from about 12 toabout 16 carbon atoms. Examples of suitable hydrocarbons are decane,dodecane, tetradecane, tridecane and mixtures thereof.

Volatile silicones useful as an active conditioning component in thecompositions of the present invention include silicone fluids such ascyclic and linear polydimethylsiloxanes. The number of silicon atoms inthe cyclic silicones is preferably from about 3 to about 7, morepreferably 4 or 5.

The general formula for the cyclic silicones is ##STR8## wherein n=3-7.The linear polydimethylsiloxanes have from about 3 to 9 silicon atomsand have the general formula:

    (CH.sub.3).sub.3 Si--O-- --Si(CH.sub.3).sub.2 --O--!.sub.n --Si(CH.sub.3).sub.3 n=1-7.

Silicones of the above type, both cyclic and linear, are available fromDow Corning Corporation, Dow Corning 344, 345 and 200 fluids; UnionCarbide, Silicone 7202 and Silicone 7158; and Stauffer Chemical,SWS-03314.

The linear volatile silicones generally have viscosities of less thanabout 5 centipoise at 25° C. while the cyclic materials have viscositiesless than about 10 centipoise at 25° C. A description of volatilesilicones is found in Todd and Byers, "Volatile Silicone Fluids forCosmetics", Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32,incorporated herein by reference.

The volatile agent may be present in the compositions of this inventionat a level of from about 1% to about 20%, preferably from about 2% toabout 15%. The volatile silicones are the preferred volatile agents.

Nonvolatile silicone fluids are useful as the active hair conditioningcomponent in the compositions of the present invention. They willgenerally have a viscosity in excess of 10 centipoise at 25° C. Examplesof such materials include polydimethylsiloxanes (fluids and gums)aminosilicones and phenylsilicones. These include polyalkyl or polyarylsiloxanes with the following structure: ##STR9## wherein R is alkyl oraryl, and x is an integer from about 7 to about 8,000 may be used. Arepresents groups which block the ends of the silicone chains.

The alkyl or aryl groups substituted on the siloxane chain (R) or at theends of the siloxane chains (A) may have any structure as long as theresulting silicones remain fluid at room temperature, are hydrophobic,are neither irritating, toxic nor otherwise harmful when applied to thehair, are compatible with the other components of the composition, arechemically stable under normal use and storage conditions, and arecapable of being deposited deposited on and of conditioning hair.

Suitable A groups include methyl, methoxy, ethoxy, propoxy, and aryloxy.The two R groups on the silicone atom may represent the same group ordifferent groups. Preferably, the two R groups represent the same group.Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyland phenylmethyl. The preferred silicones are polydimethyl siloxane,polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxaneis especially preferred.

Suitable methods for preparing these silicone materials are disclosed inU.S. Pat. Nos. 2,826,551 and 3,964,500 and references cited therein.Silicones useful in the present invention are also commerciallyavailable. Suitable examples include Viscasil, a trademark of theGeneral Electric Company and silicones offered by Dow CorningCorporation and by SWS Silicones, a division of Stauffer ChemicalCompany.

Other useful silicone materials include materials of the formula:##STR10## in which x and y are integers which depend on the molecularweight, the average molecular weight being approximately between 5,000and 10,000. This polymer is also known as "amodimethicone".

Other silicone cationic polymers which can be used in the presentcomposition correspond to the formula:

    (R.sub.1).sub.a G.sub.3-a --Si--(--OSiG.sub.2)n--(OSiG.sub.b (R.sub.1).sub.2-b).sub.m --O--SiG.sub.3-a (R.sub.1).sub.a

in which G is chosen from the group consisting of hydrogen, phenyl, OH,C₁ -C₈ alkyl and preferably methyl; a denotes 0 or an integer from 1 to3, and preferably equals 0;

b denotes 0 or 1 and preferably equals 1; the sum n+m is a number from 1to 2,000 and preferably from 50 to 150, n being able to denote a numberfrom 0 to 1,999 and preferably from 49 to 149 and m being able to denotean integer from 1 to 2,000 and preferably from 1 to 10;

R₁ is a monovalent radical of formula C_(q) H_(2q) L in which q is aninteger from 2 to 8 and L is chosen from the groups

--N(R₂)CH₂ --CH₂ --N(R₂)₂

--N(R₂)₂

--N⁺ (R₂)₃ A⁻

--N⁺ (R₂)₂ CH₂ --CH₂ --N⁺ (R₂)₃ A⁻

in which R₂ is chosen from the group consisting of hydrogen, phenyl,benzyl, a saturated hydrocarbon radical, preferably an alkyl radicalcontaining from 1 to 20 carbon atoms, and A⁻ denotes a halide ion.

These compounds are described in greater detail in European PatentApplication EP 95,238. An especially preferred polymer corresponding tothis formula is the polymer known as "trimethylsilylamodimethicone" offormula: ##STR11##

Compositions of the present invention including this material typicallywill comprise up to about 1.0% of the trimethylsilyl amodimethiconesilicone conditioning material.

Other silicone cationic polymers may also be used in the presentcompositions, such as those of the formula: ##STR12## in which R₃denotes a monovalent hydrocarbon radical having from 1 to 18 carbonatoms, and more especially an alkyl or alkenyl radical such as methyl;

R₄ denotes a hydrocarbon radical such as, preferably a C₁ -C₁₈ alkyleneradical or a C₁ -C₁₈, and preferably C₁ -C₈, alkyleneoxy radical;

Q⁻ is a halide ion, preferably chloride;

r denotes an average statistical value from 2 to 20, preferably from 2to 8;

s denotes an average statistical value from 20 to 200, and preferablyfrom 20 to 50.

These compounds are described in greater detail in U.S. Pat. No.4,185,017.

A polymer of this class which is especially preferred is that sold byUNION CARBIDE under the name "UCAR SILICONE ALE 56".

Silicone conditioning agents are used in the present compositions atlevels of from about 0.1% to about 18%, preferably from about 0.5% toabout 15%.

Preferred silicone conditioning agents for use in the presentcompositions comprise combinations of volatile silicone fluids havingviscosities of less than about 10 centipoise, and from about 0.015% toabout 9.0%, preferably from about 0.5% to about 2.0%, of silicone gumshaving viscosities of greater than about 1,000,000 centipoise, at ratiosof volatile fluid to gum of from about 90:10 to about 10:90, preferablyfrom about 85:15 to about 50:50.

Alternative preferable nonvolatile silicone materials for use in thepresent invention comprise non-volatile silicone fluids havingviscosities of less that about 100,000 cP (centipoise) at 25° C., andfrom about 0.015% to about 9.0%, preferably from about 0.5% to about2.0%, of silicone gums having viscosities greater than about 1,000,000cP at 25° C., especially polydimethylsiloxane gums andpolyphenylmethylsiloxane gums, at ratios of non-volatile fluid to gum offrom about 70:30 to about 30:70, preferably from about 60:40 to about40:60.

The efficacy of nonvolatile silicone hair conditioning agents can beenhanced through the use of silicone resin which is miscible with thesilicone hair conditioning agent. Silicone resins are highly crosslinkedpolymeric siloxane systems. The crosslinking is introduced through theincorporation of trifunctional and tetrafunctional silanes withmonofunctional or difunctional, or both, monomer units duringmanufacture of the silicone resin. As is well understood in the art, thedegree of crosslinking that is required in order to result in a siliconeresin will vary according to the specific silane units incorporated intothe silicone resin. In general, silicone materials which have asufficient level of trifunctional and tetrafunctional siloxane monomerunits (and hence, a sufficient level of crosslinking) such that they drydown to a rigid, or hard, film are considered to be silicone resins. Theratio of oxygen atoms to silicon atoms is indicative of the level ofcrosslinking in a particular silicone material. Silicone resins willgenerally have at least about 1.1 oxygen atoms per silicon atom.Preferably, the ratio of oxygen:-silicon atoms is at least about1.2:1.0. Typical silanes used in the manufacture of silicone resins aremonomethyl-, dimethyl-, monophenyl-, diphenyl-, methylphenyl-,monovinyl-, and methyl-vinyl-chlorosilanes, and tetrachlorosilane.Preferred resins are the methyl substituted silicone resins, such asthose offered by General Electric as GE SS4230 and SS4267. Commerciallyavailable silicone resins will generally be supplied in an unhardenedform in a low viscosity volatile or nonvolatile silicone fluid. Thesilicone resins for use herein should be supplied and incorporated intothe present compositions in such non-hardened form rather than as ahardened resin, as will be readily apparent to those skilled in the art.

The weight ratio of the nonvolatile silicone fluid conditioningcomponent to the silicone resin component is preferably from about 4:1to about 400:1. More preferably such ratio is from about 9:1 to about200:1, most preferably from about 19:1 to about 100:1, particularly whenthe silicone fluid component is a polydimethylsiloxane fluid or amixture of polydimethylsiloxane fluid and polydimethylsiloxane gum, asdescribed above.

Other active hair care materials for use with the vehicle systems of thepresent invention are silicone polymer materials which provide bothstyle retention and conditioning benefits to the hair. These includesilicone polymers that are rigid silicone polymers. Such materials aredescribed in U.S. Pat. No. 4,902,499, Bolich et al., issued Feb. 20,1990, incorporated herein by reference.

Additional cationic conditioning materials may be used in the presentcompositions. In general, cationic surfactants useful as hairconditioning agents include both quaternary ammonium and amine cationicsurfactant materials. If such a material other than the secondarythickener component is included in the present compositions it willgenerally be present at levels up to about 2.5%, preferably at fromabout 0.5% to about 2.0%, by weight of the composition.

Cationic surfactants that can be used, in general, contain amino orquaternary ammonium hydrophilic moieties which are positively chargedwhen dissolved in the aqueous composition of the present invention.Cationic surfactants among those useful herein are disclosed in thefollowing documents, all incorporated by reference herein: M. C.Publishing Co., McCutcheon's. Detergents& Emulsifiers, (North AmericanEdition 1979); Schwartz, et al., Surface Active Agents, Their Chemistryand Technology, New York: Interscience Publishers, 1949; U.S. Pat. No.3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No. 3,929,678,Laughlin, et al., issued Dec. 30, 1975; U.S. Pat. No. 3,959,461, Bailey,et al., issued May 25, 1976; and U.S. Pat. No. 4,387,090, Bolich, Jr.,issued Jun. 7, 1983.

Specific quaternary ammonium salts include dialkyldimethylammoniumchlorides, wherein the alkyl groups have from about 12 to about 22carbon atoms and are derived from long-chain fatty acids, such ashydrogenated tallow fatty acid (tallow fatty acids yield quaternarycompounds wherein R₁ and R₂ have predominately from 16 to 18 carbonatoms). Examples of quaternary ammonium salts useful in the presentinvention include ditallowdimethyl ammonium chloride, ditallowdimethylammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride,di(hydrogenated tallow)dimethyl ammonium chloride, dioctadecyl dimethylammonium chloride, dieicosyl dimethyl ammonium chloride, didocosyldimethyl ammonium chloride, di(hydrogenated tallow)dimethyl ammoniumacetate, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethylammonium acetate, ditallow dipropyl ammonium phosphate, ditallowdimethyl ammonium nitrate, di(coconutalkyl)dimethyl ammonium chloride,and stearyl dimethyl benzyl ammonium chloride. Ditallow dimethylammonium chloride, dicetyl dimethyl ammonium chloride, and stearyldimethyl benzyl ammonium chloride are commonly used quaternary ammoniumsalts.

Salts of primary, secondary and tertiary fatty amines are also preferredcationic surfactant materials for use herein. The alkyl groups of suchamines preferably have from about 12 to about 22 carbon atoms, and maybe substituted or unsubstituted. Secondary and tertiary amines arepreferred, tertiary amines are particularly preferred. Such amines,useful herein, include stearamido propyl dimethyl amine, diethyl aminoethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine,tri(decyl)amine, ethyl stearylamine, ethoxylated (2 moles E.O.)stearylamine, dihydroxyethyl stearylamine, and arachidylbehenylamine.Suitable amine salts include the halogen, acetate, phosphate, nitrate,citrate, lactate and alkyl sulfate salts. Such salts includestearylamine hydrochloride, soyamine chloride, stearylamine formate,N-tallowpropane diamine dichloride and stearamidopropyl dimethylaminecitrate. Cationic amine surfactants included among those useful in thepresent invention are disclosed in U.S. Pat. No. 4,275,055, Nachtigal,et al., issued Jun. 23, 1981, incorporated by reference herein.

A particular category of cationic quaternary ammonium surfactants thatcan be advantageously incorporated into the present compositions incombination with the above-described essential unsaturated quaternaryammonium surfactants, are water-insoluble materials having the formula,in salt form: ##STR13## wherein X is a salt-forming anion as previouslydescribed, a is the charge of the anion X, the radicals R₁, R₂, R₃, andR₄ independently are C₁ -C₆ alkyl, C₂₀ -C₂₂ alkyl, or benzyl wherein oneof said radicals is C₂₀ -C₂₂ alkyl, preferably C₂₂, from two to three ofsaid radicals are C₁ -C₆ alkyl, preferably C₁ -C₃, more preferablymethyl, and zero or one of said radicals is benzyl.

The long chain alkyl (i.e. the C₂₀ -C₂₂ alkyl) can be either saturatedor unsaturated. If it is unsaturated, the surfactant may also fallwithin the scope of the essential unsaturated quaternary ammoniumsurfactant thickener described above. If that is the case, it should beincluded as part of the unsaturated quaternary ammonium surfactantthickener in any assessment of the compositions hereof.

A quaternary ammonium surfactant of Formula III particularlycontemplated herein is: dimethyl behenyl benzyl ammonium salt(alternately referred to as behenalkonium salt), available from WitcoChemical Corp. (Memphis, Tenn., U.S.A.) as a chloride salt under thetrade name KEMAMINE BQ-2802C. Another particularly contemplated FormulaIII material is dimethyl arachidyl benzyl ammonium salt.

The quaternary ammonium surfactant of Formula III is generally used at alevel of from about 0.02% to about 10.0%, preferably from about 0.05% toabout 3.0%, more preferably from about 0.05% to about 2.0%, by weight,of the composition.

Preferred combinations are compositions containing the surfactant ofFormula III, especially in saturated form, in combination with thesurfactants of Formulas I or II, or a mixture thereof, wherein theFormula I and II component comprises C₁₄ -C₁₈ unsaturated alkyls,preferably at a weight ratio of (Formulas I and II):(Formula III) ofabout 1:1 to about 4:1.

A particularly useful combination of cationic surfactants that can beused comprises a mixture of di(unsaturated) C₁₆ -C₁₈ alkyl (preferablytallow) dimethyl ammonium salt (e.g. the chloride salt as commerciallyavailable from Sherex Chemicals under the tradename ADOGEN 470)) anddimethyl (saturated or unsaturated behenyl and/or arachidyl, preferablysaturated) benzyl ammonium salt (e.g. the chloride salt, at a weightratio of about 1:1 at about 4:1, more preferably about 1:1 to about 3:1.

These combinations of cationic surfactants can provide improved overallperformance for hair styling/conditioning products especially for ashair rinse products containing a styling/conditioning copolymer. Whereasthe unsaturated quaternary ammonium surfactant thickener component,especially the preferred dimethyl, di(C₁₆ -C₁₈) alkyl-substitutedsurfactants, can provide products with excellent rheology, hairconditioning, and style hold, style hold can be improved through the useof the long chain C₂₀ -C₂₂ alkyl-substituted materials of Formula IIIwhile retaining the excellent rheology and conditioning benefits of theunsaturated thickener component.

Hydrolyzed animal protein hair conditioning agents may also be includedin the present compositions. Such materials are present in thecompositions at levels of from about 0.1% to about 1.5%. An example of acommercially available material is sold under the tradename Crotein Q®from Croda, Inc.

Fatty alcohols are known hair conditioning agents and may be included inthe present compositions. However, as described supra such materialstend to deposit on hair and leave hair feeling dirty after use. Hence,it may be described that any fatty alcohol materials included in thecompositions of the present invention be present at levels no greaterthan about 1%.

Combinations of the aforementioned conditioning agents may also be usedin the present compositions.

Hair Setting Aqent

The compositions of the present invention also can contain an effectiveamount of a hair setting agent to impart styling benefits uponapplication to hair. The term "hair setting agent" means a hair settingpolymer and any carrier or diluent, not including the diluent of thevehicle system described above, that may be used in conjunction with thepolymer. As used herein, "hair styling polymer" means any polymer,natural or synthetic, that can provide hair setting benefits. Polymersof this type are well known in the art. Generally, the level of hairstyling polymer used will be at least about 0.05%, by weight, of thecomposition. Typically, it will be present at a level of from about 0.1%to about 10%, preferably from about 0.5% to about 8%.

The hair styling polymers hereof can be homopolymers, copolymers,terpolymers, etc. As used herein, the term "polymer" shall encompass allof such types of polymeric materials. For convenience in describing thepolymers hereof, monomeric units present in the polymers may be referredto as the monomers from which they can be derived. The monomers can beionic (e.g., anionic, cationic, amphoteric, zwitterionic) or nonionic.

Examples of anionic monomers include:

(i) unsaturated carboxylic acid monomers such as acrylic acid,methacrylic acid, maleic acid, maleic acid half ester, itaconic acid,fumaric acid, and crotonic acid;

(ii) half esters of an unsaturated polybasic acid anhydride such assuccinic anhydride, phthalic anhydride or the like with a hydroxylgroup-containing acrylate and/or methacrylate such as hydroxyethylacrylate and, hydroxyethyl methacrylate, hydroxypropyl acrylate and thelike;

(iii) monomers having a sulfonic acid group such as styrenesulfonicacid, sulfoethyl acrylate and methacrylate, and the like; and

(iv) monomers having a phosphoric acid group such as acidphosphooxyethyl acrylate and methacrylate, 3-chloro-2-acidphosphooxypropyl acrylate and methacrylate, and the like.

Examples of cationic monomers include:

(i) monomers derived from acrylic acid or methacrylic acid, which isreferred to hereinafter collectively as (meth)acrylic acid, and aquaternarized epihalohydrin product of a trialkylamine having 1 to 5carbon atoms in the alkyl such as (meth)acryloxypropyltrimethylammoniumchloride and (meth)acryloxypropyl-triethylammonium bromide;

(ii) amine derivatives of (meth)acrylic acid or amine derivatives of(meth)acrylamide derived from (meth)acrylic acid or (meth)acrylamide anda dialkylalkanolamine having C₁ -C₄ alkyl groups such asdimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate,dimethylaminopropyl (meth)acrylate, or dimethylaminopropyl(meth)acrylamide; and

(iii) derivatives of the products of the group (ii) above by (1)neutralization with an acid such as hydrochloric acid, or lactic acid,(2) modification with a halogenated alkyl, such as methyl chloride,ethyl chloride, methyl bromide, or ethyl iodide, (3) modification with ahalogenated fatty acid ester such as ethyl monochloroacetate, or methylmonochloropropionate, and (4) modification with a dialkyl sulfate suchas dimethyl sulfate, or diethyl sulfate.

Further cationic unsaturated monomers include amine derivatives of allylcompounds such as diallyldimethylammonium chloride and the like.

The cationic unsaturated monomers can be polymerized in cationic form.As an alternative, they can be polymerized in the form of their nonionicprecursors, which are optionally modified to be cationic, for example,by a quaternizing agent (e.g. ethyl monochloroacetate, dimethyl sulfate,etc.).

Examples of the amphoteric monomers include zwitterionized derivativesof the aforementioned amine derivatives of (meth)acrylic acids or theamine derivatives of (meth)acrylamide such as dimethylaminoethyl(meth)acrylate, dimethylaminopropyl(meth)acrylamide by a halogenatedfatty acid salt such as potassium monochloroacetate, sodiummonobromopropionate, aminomethylpropanol salt of monochloroacetic acid,triethanolamine salts of monochloroacetic acid and the like; and aminederivatives of (meth)acrylic acid or (meth)acrylamide, as discussedabove, modified with propanesultone.

These amphoteric monomers, like the aforementioned cationic monomers,can be polymerized in amphoteric form or, as an alternative, they canalso be polymerized in the form of their precursors, which are thenoptionally converted into the amphoteric state.

Preferred ionic monomers include acrylic acid, methacrylic acid,dimethylaminoethyl methacrylate, quaternized dimethylaminoethylmethacrylate, maleic acid, maleic anhydride half esters, crotonic acid,itaconic acid, diallyldimethyl ammonium chloride, polar vinylheterocyclics such as vinyl imidazole, vinyl pyridine, styrenesulfonate, and mixtures thereof. Especially preferred ionic monomersinclude acrylic acid, dimethylaminoethyl methacrylate, quaternizeddimethylaminoethyl methacrylate, and mixtures thereof.

The hair setting polymers hereof will generally comprise from 0% to 100%ionic monomers and from 0% to 100% nonionic monomers, preferably fromabout 2% to about 75% ionic monomers and from about 25% to about 98%nonionic monomers, more preferably from about 5% to about 50% ionicmonomers and from about 50% to about 95% nonionic monomers.

Representative examples of low polarity nonionic monomers are acrylic ormethacrylic acid esters of C₁ -C₂₄ alcohols, such as methanol, ethanol,1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol,2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol,3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol,3-methyl-1-pentanol, t-butanol, cyclohexanol, 2-ethyl-1-butanol,3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol,2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol,1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, and the like, thealcohols having from about 1-24 carbon atoms with the average number ofcarbon atoms preferably being from about 4-18, more preferably fromabout 4-12; styrene; chlorostyrene; vinyl esters such as vinyl acetate;vinyl chloride; vinylidene chloride; acrylonitrile; alpha-methylstyrene;t-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene; alkoxyalkyl (meth)acrylate, such as methoxy ethyl(meth)acrylate, butoxyethyl (meth)acrylate; and mixtures thereof. Othernonionic monomers include acrylate and methacrylate derivatives such asallyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate,and methacrylate, oleyl acrylate and methacrylate, benzyl acrylate andmethacrylate, tetrahydrofurfuryl acrylate and methacrylate, ethyleneglycol di-acrylate and -methacrylate, 1,3-butyleneglycol di-acrylate and-methacrylate, diacetonacrylamide, isobornyl (meth)acrylate, and thelike.

Preferred nonionic monomers include n-butyl methacrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate, methyl methacrylate,t-butylacrylate, t-butylmethacrylate, and mixtures thereof.

Representative polar nonionic monomers include acrylamide,N,N-dimethylacrylamide, methacrylamide, N-t-butyl acrylamide,methacrylonitrile, acrylate, and methacrylate alcohols (e.g. C₂ -C₆acrylate and methacrylate alcohols such as hydroxyethyl acrylate,hydroxyproxyl acrylate, hydroxyethyl methacrylate, and hydroxypropylmethacrylate), vinyl pyrrolidone, vinyl ethers, such as methyl vinylether, acyl lactones, vinyl pyridine, allyl alcohols, vinyl alcohols andvinyl caprolactam.

Examples of anionic hair styling polymers are copolymers of vinylacetate and crotonic acid, terpolymers of vinyl acetate, crotonic acidand a vinyl ester of an alpha-branched saturated aliphaticmonocarboxylic acid such as vinyl neodecanoate; and copolymers of methylvinyl ether and maleic anhydride (molar ratio about 1:1) wherein suchcopolymers are 50% esterified with a saturated aliphatic alcoholcontaining from 1 to 4 carbon atoms such as ethanol or butanol; andacrylic copolymers and terpolymers containing acrylic acid ormethacrylic acid as the anionic radical containing moiety such ascopolymers with methacrylic acid, butyl acrylate, ethyl methacrylate,etc. Another example of an acrylic polymer which can be employed in thecompositions of the present invention is a polymer of tertiary-butylacrylamide, acrylic acid, and ethyl acrylate.

An example of an amphoteric polymer which can be used in the presentinvention is Octylacrylamide/Acrylates/Butylaminoethyl MethacrylateCopolymer, described generally in U.S. Pat. No. 4,192,861 as being apolymer of N-tert-octyl acrylamide, methyl methacrylate, hydroxypropylmethacrylate, acrylic acid and t-butyl aminoethyl methacrylate, ofappropriate molecular weight for purposes hereof.

Examples of cationic hair styling polymers are copolymers ofamino-functional acrylate monomers such as lower alkylamino alkylacrylate or methacrylate monomers such as dimethylaminoethylmethacrylate with compatible monomers such asN-vinylpyrrolidone or alkyl methacrylates such as methyl methacrylateand ethyl methacrylate and alkyl acrylates such as methyl acrylate andbutyl acrylate. Cationic polymers containing N-vinylpyrrolidone arecommercially available from GAF Corp.

Still other organic, hair styling polymers include carboxymethylcellulose, copolymers of PVA and crotonic acid, copolymers of PVA andmaleic anhydride, sodium polystyrene sulfonate,PVP/ethylmethacrylate/methacrylic acid terpolymer, vinylacetate/crotonic acid/vinyl neodecanoate copolymer,octylacrylamide/acrylates copolymer, monoethyl ester of poly(methylvinyl ether-maleic acid), and octylacrylamide/acrylate/butylaminoethylmethacrylate copolymers. Mixtures of polymers may also be used.

Highly preferred active hair care materials for use with the vehiclesystems of the present invention are hair holding/styling polymers. Anyof the silicone-containing hair styling polymers known in the art forthis purpose can be used.

In its broadest sense, the silicone-containing polymers useful in thecompositions of the present invention include all copolymers of siliconewith a non-silicone adhesive polymer which: (a) when dried, thecopolymer phase-separates into a discontinuous phase which includes thesilicone portion and a continuous phase which includes the non-siliconeportion; and (b) the silicone portion is covalently attached to thenon-silicone portion. The silicone-containing polymers hereof are suchthat when formulated into the finished hair care composition, whendried, the polymer phase separates into a discontinuous phase whichincludes the polydimethylsiloxane macromer and a continuous phase whichincludes the backbone. The phase-separating nature of the compositionsof the present invention may be determined as follows:

The polymer is cast as a solid film out of a good solvent (i.e., asolvent which dissolves both the backbone and the silicone). This filmis then sectioned and examined by transmission electron micrography.Microphase separation is demonstrated by the observation of inclusionsin the continuous phase. These inclusions should have the proper size tomatch the size of the silicone chain (typically a few hundred nm orless) and the proper density to match the amount of silicone present.This behavior is well documented in the literature for polymers withthis structure (see, for example, S. D. Smith, Ph.D. Thesis, Universityof Virginia, 1987, and references cited therein).

A second method for determining phase-separating characteristicsinvolves examining the enrichment of the concentration of silicone atthe surface of a polymer film relative to the concentration in the bulkpolymer. Since the silicone prefers the low energy air interface, itpreferentially orients on the polymer surface. This produces a surfacewhich is entirely covered by silicone even when the concentration of thesilicone by weight in the whole polymer is low (2% to 20%). This isdemonstrated experimentally by ESCA (electron spectroscopy for chemicalanalysis) of the dried film surface. Such an analysis shows a high levelof silicone and a greatly reduced level of backbone polymer when thefilm surface is analyzed. (Surface here means the first few tens ofAngstroms of film thickness.) By varying the angle of the interrogatingbeam the surface can be analyzed to varying depths.

The most preferred silicone-containing polymers comprise a vinylpolymeric backbone, preferably having a Tg or a Tm above about -20° C.and, grafted to the backbone, a polydimethylsiloxane macromer having aweight average molecular weight of from about 1,000 to about 50,000,preferably from about 5,000 to about 40,000, most preferably about10,000 to about 20,000. As used herein, the abbreviation "Tg" refers tothe glass transition temperature of the non-silicone backbone, and theabbreviation "Tm" refers to the crystalline melting point of thenon-silicone backbone, if such a transition exists for a given polymer.

Highly preferred examples of such materials are the silicone-containingcopolymers as described in the following patent applications: Ser. No.07/758,319, Torgerson, Bolich and Garbe, filed Aug. 27, 1991; and Ser.No. 07/758,320, Bolich and Torgerson, filed Aug. 27, 1991; both of whichare incorporated by reference herein, and in European Patent Application90307528.1, Hayama et al. (Publication No. 0 408 311, Jan. 16, 1991).Such polymers typically have a weight average molecular weight of atleast about 10,000, generally from about 75,000 to about 3,000,000, andalso preferably, have a Tg of at least about -20 C.

In addition to the graft copolymers described above, useful copolymersinclude block copolymers containing up to about 50% (preferably fromabout 10% to about 20%) by weight of one or more polydimethyl siloxaneblocks and one or more non-silicone blocks (preferably acrylates orvinyls).

Preferred polymers comprise a vinyl polymeric backbone having a Tg or aTm above about -20° C. and, grafted to the backbone, apolydimethylsiloxane macromer having a weight average molecular weightof from about 1,000 to about 50,000, preferably from about 5,000 toabout 40,000, most preferably about 20,000.

The silicone-containing polymers utilized as styling/conditioning agentsgenerally comprise C monomers together with monomers selected from thegroup consisting of A monomers, B monomers, and mixtures thereof, asdescribed in more detail below. These copolymers contain at least A or Bmonomers together with C monomers, and preferred copolymers contain A, Band C monomers.

Examples of useful copolymers and how they are made are described indetail in U.S. Pat. No. 4,693,935, Mazurek, issued Sep. 15, 1987, andU.S. Pat. No. 4,728,571, Clemens et al., issued Mar. 1, 1988, both ofwhich reference. These herein by reference. These copolymers arecomprised of monomers A, C and, optionally, B, which are defined asfollows. A, when used, is at least one free radically polymerizablemonomer or monomers. B, when used, comprises at least one monomercopolymerizable with A and is selected from the group consisting ofpolar (relative to A) monomers and macromers having a Tg or a Tm aboveabout -20° C. When used, B may be up to about 98%, preferably up toabout 80%, more preferably up to about 20%, of the total monomers in thecopolymer. Polar monomers include ionic monomers as well as polarnonionic monomers. Monomer C comprises from about 0.01% to about 50.0%of the total monomers in the copolymer.

Representative examples of A monomers are acrylic or methacrylic acidesters of C₁ -C₁₈ alcohols, such as methanol, ethanol, 1-propanol,2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol,3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butanol, cyclohexanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol,2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol,1-dodecanol, 1-hexadecanol, 1-octadecanol, and the like, the alcoholshaving from about 1-18 carbon atoms with the average number of carbonatoms being from about 4-12; styrene; vinyl acetate; vinyl chloride;vinylidene chloride; acrylonitrile; alpha-methylstyrene; t-butylstyrene;butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene; andmixtures thereof. Preferred A monomers include n-butyl methacrylate,isobutyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate,t-butylacrylate, t-butylmethacrylate, and mixtures thereof.

Representative examples of B monomers include acrylic acid, methacrylicacid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate,quaternized dimethylaminoethyl methacrylate, methacrylonitrile,polystyrene macromer, methacrylamide, maleic anhydride and its halfesters, itaconic acid, acrylamide, acrylate alcohols, hydroxyethylnethacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone,vinyl ethers (such as methyl vinyl ether), maleimides, acylactones,vinyl pyridine, vinyl imidazole, other polar vinyl heterocyclics,styrene sulfonate, and mixtures thereof. Preferred B monomers includeacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate,quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, andmixtures thereof. Additional suitable A and B monomers are describedabove in the discussion of non-silicone-containing polymers.

The C monomer has the general formula:

    X(Y).sub.n Si(R).sub.3-m Z.sub.m

wherein X is a vinyl group copolymerizable with the A and B monomers; Yis a divalent linking group; R is a hydrogen, lower alkyl, aryl oralkoxy; Z is a monovalent siloxane polymeric moiety having a numberaverage molecular weight of at least about 500, is essentiallyunreactive under copolymerization conditions and is pendant from thevinyl polymeric backbone, described above; n is 0 or 1; and m is aninteger from 1 to 3. C has a weight average molecular weight of fromabout 1,000 to about 50,000, preferably from about 5,000 to about40,000, most preferably from about 10,000 to about 20,000. Preferably,the C monomer has the formula: ##STR14##

In those structures, m is 1, 2 or 3 (preferably m=1); p is 0 or 1; R" isalkyl or hydrogen; q is an integer from 2 to 6; X is ##STR15## R¹ ishydrogen or --COOH (preferably R¹ is hydrogen); R² is hydrogen, methylor --CH₂ COOH (preferably R² is methyl); Z is ##STR16## R⁴ is alkyl,alkoxy, alkylamino, aryl, or hydroxyl (preferably R⁴ is alkyl); and r isan integer from about 5 to about 700 (preferably r is about 130 to about250). Particularly preferred is when p=0 and q=3.

The preferred polymers useful in the present invention generallycomprise from 0% to about 98% (preferably from about 5% to about 98%,more preferably from about 50% to about 90%) of monomer A, from 0% toabout 98% (preferably from about 7.5% to about 80%) of monomer B, andfrom about 0.1% to about 50% (preferably from about 0.5% to about 40%,most preferably from about 2% to about 25%) of monomer C. Thecombination of the A and B monomers preferably comprises from about50.0% to about 99.9% (more preferably about 60% to about 99%, mostpreferably from about 75% to about 95%) of the polymer. The compositionof any particular copolymer will help determine its formulationalproperties. For example, polymers which are soluble in an aqueousformulation preferably have the composition: from 0% to about 70%(preferably from about 5% to about 70%) monomer A, from about 30% toabout 98% (preferably from about 3% to about 80%) monomer B, and fromabout 1% to about 40% monomer C. Polymers which are dispersible have thepreferred composition: from 0% to about 70% (more preferably from about5% to about 70%) monomer A, from about 20% to about 80% (more preferablyfrom about 20% to about 60%) monomer B, and from about 1% to about 40%monomer C.

Polymers for use in the present invention include the following (theweight percents below refer to the amount of reactants added in thepolymerization reaction, not necessarily the amount in the finishedpolymer):

acrylic acid/n-butylmethacrylate/polydimethylsiloxane (PDMS)macromer-20,000 molecular weight (e.g., 10/70/20 w/w/w) (I)

N,N-dimethylacrylamide/isobutyl methacrylate/PDMS macromer-20,000molecular weight (e.g., 20/60/20 w/w/w) (II)

dimethylaminoethyl methacrylate/Isobutylmethacrylate/2ethylhexyl-methacrylate/PDMS macromer-20,000 molecularweight (e.g., 25/40/15/20 w/w/w/w) (III)

dimethylacrylamide/PDSM macromer-20,000 molecular weight (e.g., 80/20w/w) (IV)

t-butylacrylate/t-butylmethacrylate/PDMS macromer-10,000 molecularweight (e.g., 56/24/20 w/w/w) (V)

t-butylacrylate/PDMS macromer-10,000 molecular weight (e.g., 80/20 w/w)(VI)

t-butylacrylate/N,N-dimethylacrylamide/PDMS macromer-10,000 molecularweight (e.g., 70/10/20 w/w/w) (VII)

t-butylacrylate/acrylic acid/PDMS macromer-10,000 molecular weight(e.g., 75/5/20 w/w/w) (VIII).

The polysiloxane-grafted polymers can be synthetized by free radicalpolymerization of the polysiloxane-containing monomers with thenon-polysiloxane-containing monomers. The general principles of freeradical polymerization methods are well understood. See, for example,Odian, "Principles of Polymerization," 2nd edition, John Wiley & Sons,1981, pp. 179-318. The desired monomers are all placed in a reactor,along with a sufficient amount of a mutual solvent so that when thereaction is complete the viscosity of the reaction is reasonable.Typical monomer loadings are from about 20% to about 50%. Undesiredterminators, especially oxygen, are removed as needed. This is done byevacuation or by purging with an inert gas, such as argon or nitrogen.The initiator is introduced and the reaction brought to the temperatureneeded for initiation to occur, assuming thermal initiators are used.Alternatively, redox or radiation initiation can be used. Thepolymerization is allowed to proceed as long as needed for a high levelof conversion to be achieved, typically from a few hours to a few days.The solvent is then removed, usually by evaporation or by precipitatingthe polymer by addition of a nonsolvent. The polymer can be furtherpurified, as desired.

The particle size of the hair setting agent of the present compositionsmay have some effect on performance in product. This, of course, willvary from polymer to polymer and from product to product.

The hair setting polymers are preferably provided in a solvent for thepolymer, generally prior to combination with the vehicle systems of thepresent invention.

The solvent selected must be able to dissolve or disperse the particularhair styling polymer being used. Suitable solvents for use in thepresent invention, in general, include, but are not limited to, alkylalcohols (such as linalool and decyl alcohol), hydrocarbons (such asisobutane, hexane, decane, dodecane, and tridecane), hydrocarbon esters(such as C₈ -C₁₂ alkanoates, e.g. methyl decanoate, di(C₂ -C₃)alkyladipates, e.g. diisopropyl adipate, C₆ -C₁₀ alkyl acetates, e.g. octylacetate, and benzoates, e.g. butyl benzoate,), volatile siliconderivatives, especially siloxanes (such as phenyl pentamethyldisiloxane, phenethyl pentamethyl disiloxane, methoxypropyl heptamethylcyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropylpentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane), ethers, such as di(C₅ -C₇)alkylethers, and mixturesthereof. Preferred solvents include volatile silicone fluids, andmixtures of silicone fluids with ester, ether, and or hydrocarbonsolvents. The choice of solvent will depend upon the particular hairsetting polymer chosen and the diluent utilized for the vehicle system,as described above. In general, it is preferred that the hair settingpolymer solvent be dispersible, but immiscible, with the vehicle systemdiluent. Also, the hair setting polymer solvent is preferably volatileand not soluble in water. For purposes hereof, "volatile" means aboiling point, at atmospheric pressure, of less than about 300° C.,preferably from about 100° C. to about 300° C., and "not soluble inwater" means a water solubility in water at 25° C. of 0.2% or less,preferably about 0.1% or less, on a water plus solvent weight basis.

The performance of the styling polymers can be improved through theincorporation of a nonvolatile plasticizer into the stylingpolymer-solvent solution. The preferred solvents in these systems arevolatile silicone fluids in which the styling polymer is soluble ordispersible. The plasticizer will generally be present in thecompositions at a plasticizer: styling polymer weight ratio of about1:20: to about 1:1, preferably from about 1:15 to about 1:2, morepreferably from about 1:12 to about 1:2.5. As used herein, "nonvolatile"in regard to plasticizers means that the plasticizer exhibitsessentially no vapor pressure at atmospheric pressure and 25° C. Thepolymer-volatile solvent solution should not suffer from substantialplasticizer weight loss while the volatile solvent is evaporating, sincethis would reduce plasticization of the styling polymer during use. Theplasticizers for use herein should generally have boiling points ofabout 250° C. or higher. Such plasticizers are nonvolatile for purposeshereof.

The plasticizer should also be compatible with the hair stylingpolymer-volatile solvent solution. By "compatible" with respect to theplasticizer and the polymer-volatile solvent solution, it is meant thatthe plasticizer does not adversely interact with the hairstyling/conditioning copolymer, and must be miscible in said solution.In general, the nonvolatile plasticizers for use herein will be ofrelatively low water solubility. The solubility parameter of theseplasticizers will generally be between about 7 and about 10, preferablybetween about 8 and about 9 (units equal(cal/cc)^(1/2)). The solubilityparameter is defined in the Polymer Handbook 3rd Ed. (John Wiley andSons, New York), J. Brankrup and E. H. Immergut, Chapter VII, pp.519-559, as the square root of the cohesive energy density and describesthe attractive strength between molecules of the material. Solubilityparameters may be determined by direct measurement, correlations withother physical properties, or indirect calculation as set forth byImmergut.

Plasticizers are well known in the art and are generally described inKirk-Othmer Encyclopedia of Chemical Technology, second edition, Volume15, pp. 720-789 (John Wiley & Sons, Inc. New York, 1968) under the topicheading "Plasticizers", and by J. Kern Sears and Joseph R. Darby in thetext The Technology of Plasticizers (John Wiley & Sons, Inc., New York,1982), both incorporated herein by reference. See especially in theAppendix of Sears/Darby Table A.9 at pages 983-1063 where a wide varietyof plasticizers are disclosed.

The plasticizers for use herein include both cyclic and acyclicnonvolatile materials. Suitable categories of nonvolatile plasticizersinclude adipates, phthalates, isophthalates, azelates, stearates,citrates, trimellitates, silicone copolyols iso C₁₄ -C₂₂ alcohols,methyl alkyl silicones, carbonates, sebacates, isobutgrates, oleates,phosphates, myristates, ricinoleates, pelargonates, valerates, oleates,camphor, and castor oil, and silicone copolyols.

Examples of adipate plasticizers include adipic acid derivatives such asdiisobutyl adipate, bis(2-ethylhexyl)adipate, diisodecyl adipate,bis(2-butoxyethyl)adipate, and di-n-hexyl adipate.

Examples of phthalate plasticizers include phthalic acid derivativessuch as dibutyl phthalate, butyl octyl phthalate, di-n-octyl phthalate,diisooctyl phthalate, bis(2-ethylhexyl)phthalate, n-octyl n-decylphthalate, di-n-hexyl phthalate, isooctyl isodecyl phthalate, diisodecylphthalate, ditridecyl phthalate, butyl cyclohexyl phthalate, diisoctylbenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate,diphenyl phthalate, isodecyl benzyl phthalate, andbis(2-butoxyethyl)phthalate.

Isophthalate plasticizers include bis(2-ethylhexyl)isophthalate, anddiisooctyl benzyl phthalate.

Examples of azelate plasticizers include azelaic acid derivatives suchas di(2-ethylhexyl)azelate, and bis(2-ethylhexyl)azelate.

Examples of stearate plasticizers include stearic acid derivatives suchas n-butyl stearate, butyl acetoxystearate, and butoxyethyl stearate.

Examples of citrate plasticizers include citric acid derivatives such asacetyl tri-n-butyl citrate, tri-n-butyl citrate, and acetal tri-2-ethylhexyl citrate.

Examples of trimellitate plasticizers includetri-(2-ethyl-hexyl)trimellitate, and triisooctyl trimellitate.

Other examples of plasticizers include dibutyl carbonate, butyl oleate,n-butyl, butyrate, isobutyl butyrate, isopropyl butyrate, dibutylcarbonate, ethyl palmitate, isooctyl palmitate, methyl ricinoleate,butyl ricinoleate, diisooctyl sebacate, triisobutyl phosphate, isodecypelargonate, ethyl valerate, isocetyl alcohol, octododecanol, isopropylmyristate, isostearyl alcohol and methyl alkyl silicones having C₂ -C₂₀alkyl and from 1 to about 500 siloxane monomer units.

Silicone copolyols, described supra, can also be used as plasticizers.

If a plasticizer is used, the molecular weight, weight average, of thestyling polymer is preferably at least about 200,000, more preferablyfrom about 300,000 to about 800,000, most preferably from about 400,000to about 600,000.

Other preferred cationic quaternary ammonium surfactants for inclusionin the compositions hereof, as a supplemental cationic conditioningagent, are mono-long chain, tri-short chain ammonium quaternarysurfactants. Suitable surfactants of this category are those having theformula, in salt form: ##STR17## wherein X is a salt-forming anion aspreviously described, a is the charge of the anion X, R₁ is a C₁₄ -C₂₂alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, preferably C₁₆ -C₂₂alkyl, more preferably C₁₆ -C₁₈ alkyl, and R₂, R₃, and R₄ independentlyare C₁ -C₆ alkyl, or benzyl, preferably C₁ -C₃ or benzyl, morepreferably methyl or benzyl, wherein only one of the short chainradicals is benzyl. X is as previously described. The long chain radicalcan be either saturated or unsaturated. The Formula IV surfactantutilized preferably is more water-soluble than the quaternarysurfactants of Formulas I and II that are present in the composition.

These cationic surfactants are particularly useful for improving wetfeel of the compositions in formulations also containing a distributingaid. In particular, they are advantageously utilized in compositionscontaining hair styling agents, or other tacky materials, which requirea distributing aid for adequate distribution of the hair setting agentor other tacky additive.

Preferred surfactants of Formula (IV) include (a) C₁₄ -C₂₂alkyl(saturated or unsaturated)dimethyl benzyl ammonium chlorides suchas stearyl benzyl dimethyl ammonium chloride, or other salts thereof,and (b) C₁₄ -C₂₂ alkyl(saturated or unsaturated)trimethyl ammoniumchlorides, or other water soluble salts thereof. Preferred are C₁₄ -C₂₂unsaturated alkyl trimethyl ammonium chloride, commercially available inAdogen 471™ from Sherex Chemical Co. (Dublin, Ohio, U.S.A.). It is alsocontemplated to use combinations of (a) and (b), preferably with C₁₆-C₁₈ alkyl chains. Alternatively, other short chain alkyls can replacemethyl (e.g. C₂ -C₆ alkyls, preferably C₂ -C₃) although methyl ispreferred. The weight ratio of (a) to (b) is preferably from about 0.5:1to 8:1, more preferably from about 1:1 to about 5:1, most preferablyfrom about 1.5:1 to about 4:1.

Surfactants of the type described by Formula (IV) are generally used ata total level of from about 0.05% to about 1.0% by weight of thecomposition, preferably from about 0.1% to about 0.75%, more preferablyfrom about 0.1% to about 0.4%. Also, preferably, the ratio of formula Iplus II surfactants to Formula IV surfactants is from about 1:20 toabout 20:1, more preferably from about 1:1 to about 15:1, morepreferably from about 2:1 to about 10:1.

These additional active cosmetic materials are generally present at atotal level of from about 0% to about 20%, preferably from about 0.1% toabout 20%, by weight of the cosmetic composition. For purposes hereof,these additional active cosmetic components shall not include theunsaturated quaternary ammonium surfactants which are encompassed byFormulas I and II, even though such surfactants generally will havecosmetic efficacy, eg. as hair or skin conditioners. The 0% levelreflects the situation when one of the vehicle component provides thehair care activity to the present compositions. For example, if thevehicle system comprises a water-insoluble quaternary ammonium compound,this material will provide hair conditioning benefits as well. The levelof the active cosmetic care material varies depending upon which activematerial is chosen, the particular cosmetic compositions to beformulated therewith, and the level of benefit desired.

Other optional components that can be added to the cosmetic compositionsof the present invention do not provide any direct cosmetic care benefitbut instead enhance the composition in some way. Examples of suchmaterials are coloring agents, such as any of the FD&C or D&C dyes;opacifiers, pearlescent aids, such as ethylene glycol distearate or TiO2coated mica; pH modifiers, such as citric acid, succinic acid,phosphoric acid, sodium hydroxide, and sodium carbonate; perservatives,such as benzyl alcohol, ethyl paraben, propyl paraben, andimidazolidonyl urea; and antioxidants. Such agents generally are usedindividually at a level of from about 0.001% to about 10%, preferablyfrom about 0.01% to about 5%, of the hair care composition. The vehiclesystems and cosmetic compositions of the present invention can be madeusing conventional formulation and mixing techniques. In one procedurefor manufacture, a silicone conditioner, quaternary ammonium surfactant,and at least a portion of the solvent component are premixed prior tothe addition of the remaining components. Methods of making varioustypes of cosmetic compositions are described more specifically in thefollowing examples.

The following examples illustrate the present invention. It will beappreciated that other modifications of the present invention within theskill of those in the cosmetic composition formulation art can beundertaken without departing from the spirit and scope of thisinvention.

All parts, percentages, and ratios herein are by weight unless otherwisespecified.

EXAMPLE I

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component            Weight %                                                 ______________________________________                                        Styling Agent Premix                                                          Silicone Copolymer.sup.1                                                                           2.00                                                     Phenylpentamethyl disiloxane                                                                       9.00                                                     Xanthan Premix                                                                Xanthan gum          0.25                                                     DRO H.sub.2 O        25.00                                                    Main Mix                                                                      Dioleyl-dimethylammonium chloride                                             (DODMAC)             0.50                                                     EDTA, disodium salt  0.10                                                     D.C. 929.sup.2       2.00                                                     Perfume              0.10                                                     Natrosol Plus CS Grade D-67.sup.3                                                                  0.75                                                     Locust bean gum      0.15                                                     Kathon CG.sup.4      0.04                                                     DRO H.sub.2 O        q.s. to 100%                                             ______________________________________                                         .sup.1 20/60/20 N,Ndimethylacrylamide/isobutyl methacrylate/PDMS macromer     (20,000 MW), polymer molecular weight about 300,000.                          .sup.2 Amodimethicone, commercially available from Dow Corning                .sup.3 Hydrophobically modified hydroxethylcellulose having a C.sub.16        alkyl substitution of from about 0.50% to about 0.95%, by weight, and a       hydroxyethyl molar substitution of from about 2.3 to about 3.3, and where     the average molecular weight of the hydroxyethyl cellulose prior to           substitution is approximately 700,000, available from Aqualon Company.   

The composition is prepared as follows. The DRO (double reverse osmosis)water is first heated to 71° F. The DODMAC, EDTA, and D.C. 929 are addedto the water and mixed for about 5 minutes. The Natrosol is added to thecomposition with mixing. The Locust Bean Gum is added to the compositionwith mixing. The composition is then homogenized with a disperser, forexample a Gifford-Wood mill, for about 2 minutes. The batch is thencooled to 38° F. The xanthan gum premix, styling agent premix, perfumeand Kathan CG are added to the composition with mixing for about 10minutes. The batch is cooled to ambient temperature and stored.

EXAMPLE II

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component             Weight %                                                ______________________________________                                        Styling Agent Premix                                                          Silicone Copolymer.sup.1                                                                            3.00                                                    Phenylpentamethyl disiloxane                                                                        9.00                                                    Hydroxypropylpentamethyl disiloxane                                                                 6.00                                                    Silicone Gum Premix                                                           Silicone Gum G.E. SE 76.sup.2                                                                       0.50                                                    Decamethyl cyclopentasiloxane                                                                       4.00                                                    Main Mix                                                                      Natrosol Plus CS Grade D-67.sup.3                                                                   0.60                                                    Locust bean gum       0.50                                                    EDTA, disodium salt   0.15                                                    ADOGEN 470.sup.5      0.65                                                    Glydant.sup.4         0.40                                                    Perfume               0.20                                                    DRO H.sub.2 O         q.s. to 100%                                            ______________________________________                                         .sup.1 10/70/20 acrylic acid/nbutyl methacrylate/silicone macromer, the       macromer having a molecular weight of about 20,000, prepared in a manner      similar to Example C2c of U.S. Pat. No. 4,728,571, Clemens, issued March      1, 1988, polymer molecular weight about 300,000                               .sup.2 Commercially available from General Electric                           .sup.3 hydrophobicallymodified hydroxyethyl cellulose commercially            available from Aqualon Co.                                                    .sup.4 preservative commercially available from Glyco, Inc.                   .sup.5 Partially hydrogenated ditallow dimethyl ammonium chloride,            commercially available from Sherex Chemical Company, Dublin, Ohio, USA.  

The composition is prepared as follows. The DRO water is heated to 71°F. The ADOGEN 470, EDTA, and silicone gum premix are added to the waterwith mixing for about 5 minutes. The Natrosol is added with mixing. TheLocust Bean Gum is added with mixing. The composition is thenhomogenized with a disperser, for example a Gifford-Wood mill, for about2 minutes. The batch is cooled to 38° F. and the styling agent premix,the perfume and the Glydant are added with mixing for about 10 minutes.The batch is cooled to ambient temperature and stored.

EXAMPLE III

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component            Weight %                                                 ______________________________________                                        Natrosol Plus CS Grade D-67.sup.1                                                                  1.20                                                     Xanthan Gum          0.25                                                     Citric Acid          0.073                                                    Sodium Citrate       0.175                                                    Kathon CG            0.033                                                    ADOGEN 470.sup.3     0.75                                                     Hydrogenated Tallow Betaine                                                                        0.33                                                     Styling Agent Premix                                                          T-Butyl Acrylate/PDMS Copolymer                                               (10,000 MW - 80/20 W/W)                                                                            2.50                                                     Phenethyl Pentamethyl Disiloxane                                                                   1.875                                                    D4 Cyclomethicone    5.625                                                    Silicone Premix                                                               Polydimethyl Siloxane Gum/                                                    D5 Cyclomethicone (15/85).sup.2                                                                    2.333                                                    Perfume              q.s.                                                     DRO Water            q.s. to 100%                                             ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethyl cellulose available from         Aqualon Corp.                                                                 .sup.2 G.E. SE76 gum available from G.E. Silicones                            .sup.3 Partially hydrogenated ditallow dimethyl ammonium chloride,            commercially available from Sherex Chemical Company, Dublin, Ohio, USA   

The composition is prepared as follows. The xanthan gum is firstslurried in water at 4% xanthan gum, until fully hydrated. In a separatevessel the copolymer is mixed into the phenethyl pentamethyl disiloxaneand D4 cyclomethicone.

The remaining water is preheated to about 71° C. The ADOGEN 470, citricacid, sodium citrate, and hydrogenated tallow betaine are added to thewater and mixed until melted. This mixture is then cooled to about 65°C. The Natrosol Plus, silicone gum premix, Kathon and perfume are addedand mixed until homogeneous. This mixture is then cooled to about 38° C.The xanthan gum premix and copolymer premix are then added and themixture is agitated until homogeneous. The resulting composition iscooled to ambient temperature.

EXAMPLE IV

The following is a hair conditioning rinse composition which isrepresentative of the present invention.

    ______________________________________                                        Component             Wt. %                                                   ______________________________________                                        Silicone Gum Premix                                                           Octamethyl Cyclotetrasiloxane                                                                       3.00                                                    G.E. SE 76.sup.2      0.50                                                    Main Mix                                                                      Natrosol Plus CS Grade D-67.sup.1                                                                   1.25                                                    Di rapeseed alkyl dimethyl ammonium                                                                 0.75                                                    chloride (DRaDMAC)                                                            Stearamide DEA        0.10                                                    Kathon CG             0.04                                                    DRO Water and fragrance                                                                             q.s. to 100%                                            ______________________________________                                         .sup.1 Hydrophobically modified hydroxethylcellulose available from           Aqualon                                                                       .sup.2 Silicone gum available from General Electric                      

The composition is prepared as follows. The DRO water is first heated to71° C. The DRaDMAC, stearamide DEA, Natrosol, and the Silicone gumpremix are added with mixing. The composition is then homogenized with adisperser, e.g., a Gifford-Wood mill, for about 2 minutes. Thecomposition is cooled to 38° C. and the Kathon and perfume are addedwith mixing for about 10 minutes. The batch is cooled to ambienttemperature and stored.

EXAMPLE V

The following is a hair styling conditioner composition which isrepresentative of the present invention.

    ______________________________________                                        Component             Wt. %                                                   ______________________________________                                        Disodium EDTA         0.15                                                    Monosodium Phosphate  0.04                                                    Disodium Phosphate    0.12                                                    ADOGEN 470.sup.4      0.75                                                    Locust Bean Gum       0.70                                                    Natrosol Plus CS Grade D-67.sup.1                                                                   0.70                                                    Glydant               0.37                                                    Xanthan Gum           0.25                                                    Perfume               0.02                                                    Water                 q.s. to 100%                                            Silicone Gum Premix                                                           G.E. S E 76.sup.2     0.50                                                    Octamethyl Cyclotetrasiloxane                                                                       3.00                                                    Styling Polymer Premix                                                        Styling Polymer.sup.3 3.00                                                    Phenyl Pentamethyl Disiloxane                                                                       9.00                                                    Hydroxypropyl Pentamethyl Disiloxane                                                                6.00                                                    ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethylcellulose available from          Aqualon                                                                       .sup.2 Silicone Gum available from General Electric                           .sup.3                                                                        Isobutylmethacrylate/2ethylhexylmethacrylate/N,N-dimethyl-acrylamide copo    ymer 80/5/15                                                                   .sup.4 Partially hydrogenated ditallow dimethyl ammonium chloride,            commercially available from Sherex Chemical Company, Dublin, Ohio, USA.  

The composition is prepared as follows. The DRO water is heated to 71°C. The ADOGEN 470, disodium EDTA, monosodium phosphate, and disodiumphosphate are added and the composition is mixed for about 5 minutes.The silicone gum premix, locust bean gum, and Natrosol are added withmixing. The composition is then homogenized using a disperser, e.g., aGifford-Wood Mill, for about 2 minutes. The batch is cooled to 38° F.and the Xanthan Gum premix, styling polymer premix, perfume and Glydantare added and mixed for about 10 minutes. The composition is then cooledto ambient temperature and stored.

EXAMPLE VI

The following is a styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component           Wt. %                                                     ______________________________________                                        Styling Agent                                                                 Silicone Copolymer.sup.1                                                                          3.00                                                      Octamethyl cyclotetrasiloxane                                                                     9.00                                                      Premix                                                                        Silicone Gum GE SE76.sup.2                                                                        0.50                                                      Decamethyl cyclopentosiloxane                                                                     4.00                                                      Main Mix                                                                      Natrosol Plus CS Grade D-67.sup.3                                                                 1.25                                                      ADOGEN 470.sup.5    0.80                                                      KEMAMINE Q-1902C.sup.6                                                                            0.40                                                      Kathon CG.sup.4     0.03                                                      Imidazole           0.15                                                      Perfume             0.10                                                      DRO H.sub.2 O       q.s. to 100%                                              ______________________________________                                         .sup.1 80/20 tbutyacrylate/PDMS macromer, the macromer having a molecular     weight of about 10,000, prepared in a manner similar to Example C2b of        U.S. Pat. No. 4,728,571, Clemens issued March 1, 1988.                        .sup.2 Commercially available from General Electric                           .sup.3 hydrophobicallymodified hydroxyethyl cellulose commercially            available from Aqualon Co.                                                    .sup.4 preservative commercially available from Rohm & Haas                   .sup.5 Partially hydrogenated ditallow dimethyl ammonium chloride,            commercially available from Sherex Chemical Company, Dublin, Ohio, USA.       .sup.6 Dimethyl dibehenyl/diarachidyl ammonium chloride, commercially         available from Witco Chemical Corporation, Memphis, Tennessee, USA.      

The composition is prepared as follows. The Styling Agent and Premix areblended separately by conventional means. The Main Mix is prepared byadding all the ingredients and heating to 95° C. for 1/2 hour withagitation. As the batch is cooled to about 60° C., the Premix andStyling Agent mixes are added to the Main Mix with agitation and thebatch is cooled to ambient temperature.

EXAMPLE VII

The following is a hair styling composition which is representative ofthe present invention.

    ______________________________________                                        Ingredient             Wt. %                                                  ______________________________________                                        Premix 1:                                                                     G.E. SE 16 Gum.sup.1   0.80                                                   Cab-O-Sil HS-5.sup.2   0.20                                                   Decamethylcyclopentasiloxane                                                                         4.50                                                   Premix 2:                                                                     G.E. SE 76 Gum         0.50                                                   Decamethylcyclopentasiloxane                                                                         2.80                                                   Natroso Plus CS Grade D-67.sup.3                                                                     1.39                                                   Diricinoleyl dimethyl  0.50                                                   ammonium methyl sulfate (DRDMAMS)                                             Glydant.sup.4          0.37                                                   Disodium phosphate     0.12                                                   Monosodium phosphate   0.03                                                   Disodium EDTA.sup.5    0.15                                                   Fragrance              0.02                                                   DRO H.sub.2 O          q.s. to 100%                                           ______________________________________                                         .sup.1 Polydimethylsiloxane gum offered by General Electric                   .sup.2 Fumed silica offered by the Cabot Corp.                                .sup.3 Hydrophobically modified hydroxyethyl cellulose available from         Aqualon Co.                                                                   .sup.4 Preservative offered by Glyco, Inc.                                    .sup.5 Ethylene diamine tetraacetic acid                                 

The composition is prepared as follows. The DRO water is heated to 65°F. The EDTA, phosphates, and DRDMAMS are added to the water with mixingfor about 10 minutes. The Natrosol is then added with mixing for about 5minutes. The silicone gum premixes are then added with mixing. Thecomposition is then homogenized with a disperser, for example aGifford-Wood Mill, for about 2 minutes. The batch is cooled to 100° F.The Glydant and perfume are added with mixing for about 10 minutes. Thebatch is cooled to ambient temperature and stored.

EXAMPLE VIII

The following is a hair conditioner which is representative of thepresent invention.

    ______________________________________                                        Ingredient          Wt. %                                                     ______________________________________                                        Premix:                                                                       G.E. SE 76 Gum.sup.1                                                                              0.10                                                      Decamethylcyclopentasiloxane                                                                      0.60                                                      Natrosol Plus CS Grade D-67.sup.2                                                                 1.50                                                      Hydrogenated tallowamide DEA                                                                      0.70                                                      Adogen 470.sup.3    0.50                                                      Glydant.sup.4       0.37                                                      Disodium EDTA.sup.5 0.15                                                      Disodium phosphate  0.12                                                      Monosodium phosphate                                                                              0.03                                                      Fragrance           0.02                                                      DRO H.sub.2 O       q.s. to 100%                                              ______________________________________                                         .sup.1 Polydimethylsiloxane gum offered by General Electric                   .sup.2 Hydrophobically modified hydroxyethyl cellulose available from         Aqualon                                                                       .sup.3 Di partically(hydrogenated) tallow dimethyl ammonium chloride          offered by Sherex Chemical Co.                                                .sup.4 Preservative offered by Glyco, Inc.                                    .sup.5 Ethylene diamine tetraacetic acid                                 

The composition is prepared as follows. The DRO water is heated to 65°F. The EDTA, phosphates, DEA, and Adogen are added to the water withmixing for about 10 minutes. The Natrosol is then added with mixing forabout 5 minutes. The silicone gum premix is then added with mixing. Thecomposition is then homogenized with a disperser, for example aGifford-Wood Mill, for about 2 minutes. The batch is cooled to 38° F.The Glydant and perfume are added with mixing for about 10 minutes. Thebatch is cooled to ambient temperature and stored.

EXAMPLE IX

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component            Weight %                                                 ______________________________________                                        Natrosol Plus CS Grade D-67.sup.1                                                                  1.15                                                     ADOGEN 470.sup.5     0.75                                                     Citric Acid          0.07                                                     Sodium Citrate       0.17                                                     Styling Polymer Premix -                                                      Styling Polymer.sup.2                                                                              2.5                                                      Phenyl Ethyl Pentamethyl Disiloxane                                                                1.875                                                    Octamethyl Cyclotetrasiloxane                                                                      5.625                                                    Butyl Stearate       0.20                                                     Silicone Gum Premix -                                                         Polydimethyl Siloxane Gum                                                                          0.35                                                     Decamethyl Cyclopentasiloxane                                                                      1.98                                                     Kathon CG            0.033                                                    Perfume              0.2                                                      Xanthan Gum.sup.4    0.25                                                     DRO Water            q.s. to 100%                                             ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethyl cellulose available from         Aqualon Corp.                                                                 .sup.2 80/20 tButylacrylate/PDMS macromer, the macromer having a molecula     weight of about 10,000, prepared in a manner similar to Example C2b of        U.S. Pat. No. 4,728,571, Clemens, issued March 1, 1988                        .sup.3 S.E. 76 gum available from General Electric                            .sup.4 Readily dispersible xanthan gum                                        .sup.5 Partially hydrogenated ditallow dimethyl ammonium chloride,            commercially available from Sherex Chemical Company, Dublin, Ohio, USA.  

The composition is prepared as follows.

The styling polymer premix is prepared by combining the styling polymer,phenyl ethyl pentamethyl disiloxane, butyl stearate, and the octamethylcyclotetrasiloxane.

The silicone gum premix is prepared by combining, in a separate vesseland mixing the silicone gum and the decamethyl cyclopenta siloxane untilhomogeneous.

About one-half of the DRO water is first heated to about 66° C. Thecitric acid, and sodium citrate are added and mixed until homogeneous.The Natrosol and xanthan gum are added and mixed until homogeneous. Thecomposition is cooled to about 38° C. The styling polymer premix, KathonCG and perfume are added. The composition is mixed and homogenized witha homogenizer such as a Tekmar homogenizer (preferably in-line).

The remaining DRO water is heated to about 88° C., the ADOGEN 470 isadded and mixed until homogeneous. The mixture is then cooled to about43° C. The silicone gum premix is added and the composition homogenizedwith a homogenizer (in-line preferred).

The two premixes are then combined and mixed until homogeneous to formthe styling rinse composition.

EXAMPLE X

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component           Weight %                                                  ______________________________________                                        Natrosol Plus CS Grade D-67.sup.1                                                                 1.15                                                      ADOGEN 470.sup.5    0.75                                                      Stearyl Alcohol     0.2                                                       Cetyl Alcohol       0.3                                                       Citric Acid         0.07                                                      Sodium Citrate      0.17                                                      Styling Polymer Premix -                                                      Styling Polymer.sup.2                                                                             2.5                                                       Decamethyl Cyclopentasiloxane                                                                     1.815                                                     Octamethyl Cyclotetrasiloxane                                                                     5.625                                                     Silicone Gum Premix -                                                         Polydimethyl Siloxane Gum.sup.3                                                                   0.35                                                      Decamethyl Cyclopentasiloxane                                                                     1.98                                                      Kathon CG           0.033                                                     Perfume             0.2                                                       Xanthan Gum.sup.4   0.25                                                      DRO Water           q.s. to 100%                                              ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethyl cellulose available from         Aqualon Corp.                                                                 .sup.2 80/20 tButyacrylate/PDMS macromer, the macromer having a molecular     weight of about 10,000, prepared in a manner similar to Example C2b of        U.S. Pat. No. 4,728,571, Clemens, issued March 1, 1988                        .sup.3 S.E. 76 gum available from General Electric                            .sup.4 Readily dispersible xanthan gum                                        .sup.5 Partially hydrogenated ditallow dimethyl ammonium chloride,            commercially available from Sherex Chemical Company, Dublin, Ohio, USA.  

The composition is prepared as follows.

The styling polymer premix is prepared by combining the styling polymer,decamethyl cyclopentasiloxane, and the octamethyl cyclotetrasiloxane.

The silicone gum premix is prepared by combining, in a separate vesseland mixing the silicone gum and the decamethyl cyclopenta siloxane untilhomogeneous.

About one-half of the DRO water is first heated to about 66° C. Thecitric acid, and sodium citrate are added and mixed until homogeneous.The Natrosol and xanthan gum are added and mixed until homogeneous. Thecomposition is cooled to about 38° C. The styling polymer premix, KathonCG and perfume are added. The composition is mixed and homogenized witha homogenizer such as a Tekmar homogenizer (preferably in-line).

The remaining DRO water is heated to about 88° C., the ADOGEN 470stearyl alcohol and cetyl alcohol are added and mixed until homogeneous.The mixture is then cooled to about 43° C. The silicone gum premix isadded and the composition homogenized with a homogenizer (in-linepreferred).

The two premixes are then combined and mixed until homogeneous to formthe styling rinse composition.

EXAMPLE XI

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component              Weight %                                               ______________________________________                                        Natrosol Plus CS Grade D-67.sup.1                                                                    1.15                                                   ADOGEN 470.sup.5       0.75                                                   Citric Acid            0.07                                                   Sodium Citrate         0.17                                                   Styling Polymer Premix -                                                      Styling Polymer.sup.2  2.5                                                    Phenyl Ethyl Pentamethyl Disiloxane                                                                  1.875                                                  Octamethyl Cyclotetrasiloxane                                                                        5.625                                                  Silicone Gum/Fluid Premix                                                     Polydimethyl Siloxane Gum.sup.3                                                                      0.20                                                   350 centistoke Polydimethyl Siloxane Fluid                                                           0.30                                                   Kathon CG              0.033                                                  Perfume                0.2                                                    Xanthan Gum.sup.4      0.25                                                   DRO Water              q.s. to 100%                                           ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethyl cellulose available from         Aqualon Corp.                                                                 .sup.2 80/20 tButylacrylate/PDMS macromer, the macromer having a molecula     weight of about 10,000, prepared in a manner similar to Example C2b of        U.S. Pat. 4,128,571, Clemens, issued March 1, 1988                            .sup.3 S.E. 76 gum available from General Electric                            .sup.4 Readily dispersible xanthan gum                                        .sup.5 Partially hydrogenated ditallow dimethyl ammonium chloride,            commercially available from Sherex Chemical Company, Dublin, Ohio, USA.  

The composition is prepared as follows.

The styling polymer premix is prepared by combining the styling polymer,phenyl ethyl pentamethyl disiloxane, and the octamethylcyclotetrasiloxane.

The silicone gum/fluid premix is prepared by combining in a separatevessel and mixing the silicone gum and silicone fluid until homogeneous.

About one-half of the DRO water is first heated to about 66° C. Thecitric acid, and sodium citrate are added and mixed until homogeneous.The Natrosol and xanthan gum are added and mixed until homogeneous. Thecomposition is cooled to about 38° C. The styling polymer premix, KathonCG and perfume are added. The composition is mixed and homogenized witha homogenizer such as a Tekmar homogenizer (preferably in-line).

The remaining DRO water is heated to about 88° C., the ADOGEN 470 isadded and mixed until homogeneous. The mixture is then cooled to about43° C. The silicone gum/fluid premix is added and the compositionhomogenized with a homogenizer (in-line preferred).

The two premixes are then combined and mixed until homogeneous to formthe styling rinse composition.

EXAMPLE XII

The following is a hair styling rinse composition representative of thepresent invention.

    ______________________________________                                        Component           Weight %                                                  ______________________________________                                        Natrosol Plus CS Grade D-67.sup.1                                                                 1.15                                                      Hydrogenated Tallow Betaine                                                                       0.30                                                      Methyl-1-soya amido ethyl-2-soya                                                                  0.75                                                      imidazolinium (MSAESI)                                                        Citric Acid         0.07                                                      Sodium Citrate      0.17                                                      Styling Polymer Premix -                                                      Styling Polymer.sup.2                                                                             2.5                                                       Octamethyl Cyclotetrasiloxane                                                                     5.25                                                      Decamethyl Cyclopentasiloxane                                                                     2.25                                                      Silicone Gum Premix -                                                         Polydimethyl Siloxane Gum.sup.3                                                                   0.35                                                      Decamethyl Cyclopentasiloxane                                                                     1.98                                                      Kathon CG           0.033                                                     Perfume             0.2                                                       Xanthan Gum.sup.4   0.25                                                      DRO Water           q.s. to 100%                                              ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethyl cellulose available from         Aqualon Corp.                                                                 .sup.2 80/20 tButylacrylate/PDMS macromer, the macromer having a molecula     weight of about 10,000, prepared in a manner similar to Example C2b of        U.S. Pat. 4,728,571, Clemens, issued March 1, 1988                            .sup.3 S.E. 76 gum available from General Electric                            .sup.4 Readily dispersible xanthan gum                                   

The composition is prepared as follows.

The styling polymer premix is prepared by combining the styling polymer,the octamethyl tetrasiloxane, and the decamethyl pentasiloxane.

The silicone gum premix is prepared by combining, in a separate vesseland mixing the silicone gum and the decamethyl cyclopentasiloxane untilhomogeneous.

About one-half of the DRO water is first heated to about 66° C. Thehydrogenated tallow betaine, citric acid, and sodium citrate are addedand mixed until homogeneous. The Natrosol and xanthan gum are added andmixed until homogeneous. The composition is cooled to about 38° C. Thestyling polymer premix, Kathon CG and perfume are added. The compositionis mixed and homogenized with a homogenizer such as a Tekmar homogenizer(preferably in-line).

The remaining DRO water is heated to about 88° C., the MSAESI is addedand mixed until homogeneous. The mixture is then cooled to about 43° C.The silicone gum premix is added and the composition homogenized with ahomogenizer (in-line preferred).

The two premixes are then combined and mixed until homogeneous to formthe styling rinse composition.

EXAMPLES XIII-XVI

The following are hair styling/conditioning rinse compositionsrepresentative of the present invention.

    ______________________________________                                        Composition          XIII   XIV    XV   XVI                                   ______________________________________                                        Citric Acid          0.02   0.02   0.02 0.02                                  Sodium Citrate       0.09   0.09   0.09 0.09                                  Cetyl Alcohol        0.12   0.12   0.12 0.12                                  Stearyl Alcohol      0.08   0.08   0.08 0.08                                  Natrosol Plus CS Grade D-67.sup.1                                                                  1.25   1.40   0.95 1.10                                  Xanthan Gum.sup.2    0.25   0.25   0.25 0.25                                  Styling Polymer Premix                                                        Styling Polymer.sup.3                                                                              1.75   1.75   1.75 1.75                                  Octamethyl Tetrasiloxane                                                                           5.98   5.98   5.98 5.98                                  Decamethyl Pentasiloxane                                                                           2.56   2.56   2.56 2.56                                  Butyl Stearate       0.15   0.15   0.15 0.15                                  Kathon CG            0.03   0.03   0.03 0.03                                  Perfume              0.33   0.33   0.33 0.33                                  Thickener Premix                                                              DRO Water            11.67  11.90  11.93                                                                              11.63                                 Adogen 470.sup.5     0.67   1.33   1.00 1.00                                  Kemamine ® BQ-2802C                                                                            0.33   --     --   --                                    Stearyl trimethyl    --     --     0.30 --                                    ammonium chloride                                                             Adogen 471.sup.6     --     --     --   0.60                                  Silicone Gum Premix                                                           Decamethyl Pentasiloxane                                                                           1.98   1.42   1.42 1.42                                  Polydimethyl Siloxane Gum.sup.4                                                                    0.35   0.25   0.25 0.25                                  Amodimethicone (Dow Corning Q2-8220)                                                               --     0.10   0.10 0.10                                  DRO Water            q.s.   q.s.   q.s. q.s.                                  ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethyl cellulose from Aqualon Corp.     .sup.2 Readily dispersible xantham gum                                        .sup.3 80/20 tButylacrylate/PDMS macromer, the macromer having a molecula     weight of about 10,000, prepared in a manner similar to Example C2b of        U.S. Pat. 4,728,571, Clemens, issued March 1, 1988.                           .sup.4 SE76 gum available From General Electric                               .sup.5 Solution of 75% surfactant and 25% isopropyl alcohol/water for         Examples XV and XVI; 100% surfactant for Examples XIII and XIV.               .sup.6 Tallow trimethyl ammonium chloride (Sherex Chemical Co.)          

The styling polymer premix is prepared by combining the styling polymer,the octamethyl tetrasiloxane and decamethyl pentasiloxane, and butylstearate.

The silicone gum premix is prepared by combining and mixing (in aseparate vessel) the silicone gum and decamethyl pentasiloxane untilhomogeneous.

The thickener premix is prepared by combining and mixing (in a separatevessel) DRO water, and any primary and secondary thickeners (premeltedif necessary to ensure homogenity) at 82° C., and the silicone gumpremix and the amodimethicone at 71° C., until homogeneous.

In another vessel, the DRO water is heated to 71° C. Citric acid, sodiumcitrate, cetyl alcohol, stearyl alcohol and Natrosol Plus CS grade D-67are added and mixed until homogeneous. The xanthan gum is added andmixed until homogeneous. The styling polymer premix, Kathon CG andperfume are added and mixed until homogeneous. The composition isfurther dispersed with an in-line homogenizer (such as Tekmarhomogenizer) and then cooled to 38° C.

The thickener premix is also further dispersed with an in-linehomogenizer and cooled to 38° C. and added to the final vessel, mixinguntil homogeneous to form the styling rinse composition.

The compositions hereof comprise or, alternatively, can consistessentially of or consist of the essential ingredients, as well as thevarious optional ingredients, described herein.

EXAMPLES XVII-XIX

The following are hair styling/conditioning rinse compositionsrepresentative of the present invention.

    ______________________________________                                        Composition       I         II     III                                        ______________________________________                                        Conditioner Premix                                                            DRO Water         q.s.      q.s.   q.s.                                       Citric Acid       0.02      0.02   0.02                                       Sodium Citrate    0.09      0.09   0.10                                       Cetyl Alcohol     0.12      0.12   0.12                                       Stearyl Alcohol   0.08      0.08   0.08                                       Natrosol Plus CS Grade D-67.sup.1                                                               1.02      1.00   0.99                                       Xanthan Gum.sup.2 0.25      0.25   0.25                                       Styling Polymer Premix                                                        Polysiloxane-Grafted                                                          Polymer.sup.7     1.75      1.75   1.15                                       Octamethyl cyclotetrasiloxane                                                                   5.98      5.98   5.98                                       Decamethyl cyclopentasiloxane                                                                   2.56      2.56   2.56                                       Butyl Stearate    0.15      0.15   0.15                                       Trimethylsiloxysilicate                                                                         0.11      0.11   0.11                                       Kathon CG         0.03      0.03   0.03                                       Perfume           0.33      0.33   0.33                                       Silicone Premix                                                               DRO Water         9.48      9.48   8.57                                       Adogen 470.sup.4  0.70      0.60   0.93                                       Adogen 471.sup.5  0.05      0.15   0.07                                       Decamethyl cyclopentasiloxane/                                                                  1.61      1.67   2.33                                       Polydimethyl Siloxane Gum.sup.3                                               Amodimethicone    0.10      0.10   0.10                                       (Dow Corning Q2-8220).sup.6                                                   Surfactant Premix                                                             DRO Water         5.70      5.70   5.70                                       Stearalkonium Chloride                                                                          0.30      0.30   0.30                                       ______________________________________                                         .sup.1 Hydrophobically modified hydroxyethyl cellulose from Aqualon Corp.     .sup.2 Readily dispersible xantham gum                                        .sup.3 SE76 gum available from General Electric                               .sup.4 Ditallow dimethyl ammonium chloride, Sherex Chemical Co., Dublin,      Ohio, USA; 75% aqueous solution                                               .sup.5 Tallow trimethyl ammonium chloride, Sherex Chemical Co.; 50%           aqueous solution.                                                             .sup.6 Trimethylsilylamodimethicone                                           .sup.7 80 wt % tbutyl acrylate/20 wt % silicone macromer(wt average           molecular weight of 10,000), polymer weight average molecular weight of       about 1,000,000                                                          

The styling polymer premix is prepared by combining the polymer, theoctamethyl tetrasiloxane and decamethyl pentasiloxane, butyl stearate,and silicone resin.

The silicone premix is prepared by combining and mixing (in a separatevessel) water, Adogen 470 and Adogen 471 at 85° C. Cool to 71° C. andadd the silicone gum/decamethyl cyclopentasiloxane solution andAmodimethicone and mix until homogeneous. Cool to 38° C. while usinghomogenizer (such as Tekmar).

The surfactant premix is prepared by combining and mixing (in a separatevessel) water and Stearalkonium Chloride at 38° C.

The conditioner premix is prepared by combining and mixing (in aseparate vessel) the DRO water heated to 71° C. Citric acid, sodiumcitrate, cetyl alcohol, stearyl alcohol and Natrosol Plus CS grade D-67are added and mixed until homogeneous. The xanthan gum is added andmixed until homogeneous. The styling polymer premix, Kathon CG andperfume are added and mixed until homogeneous. The composition isfurther dispersed with an in-line homogenizer (such as Tekmarhomogenizer) and then cooled to 38° C.

The conditioner is completed by combining and mixing (in a separatevessel) the conditioner premix, the silicone premix and the surfactantpremix at 38° C. This mixture is then cooled to 380° C.

When the compositions defined in Examples I-III are applied to hair inthe conventional manner, they provide effective hair conditioning andstyling/hold benefits without leaving the hair with a sticky/stiff feel.

What is claimed is:
 1. A cosmetic composition useful in application tothe hair or skin, comprising:(a) from about 80% to about 100% by weightof the composition of a vehicle system which comprises:(A) from about0.1% to about 10.0% by weight of the cosmetic composition of a polymerwhich comprises a hydrophilic water-soluble polymer backbone havinggrafted thereto hydrophobic groups selected from the group consisting ofC₈ -C₂₂ alkyl, aryl alkyl, alkyl aryl groups and mixtures thereof;wherein the ratio of the hydrophilic backbone to the hydrophobic groupsof the polymer is from about 10:1 to about 1000:1; (B) from about 0.02%to about 10.0% by weight of the cosmetic composition of unsaturatedquaternary ammonium surfactant component of the formula: ##STR18##wherein X is a salt-forming anion, a is the ionic charge of X, thequaternary ammonium radicals R₁, R₂, R₃, and R₄ independently are C₁-C₂₂ alkyl, C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, or benzyl, and fromtwo to three of said quaternary ammonium radicals are C₁₄ -C₂₂ alkyl orC₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene or mixtures thereof, no more thantwo of said radicals being C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene or acombination of C₁₄ -C₂₂ alkyl and C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene,from one to two of said quaternary ammonium radicals are C₁ -C₆ alkyls,and no more than one of said radicals is benzyl; or ##STR19## wherein Xis a salt-forming anion, a is the ionic charge of X, radicals R₁, R₂,and R₃ independently are C₁ -C₂₂ alkyl or benzyl, and two or three ofsaid radicals are C₁₄ -C₂₂ alkyl, or C₁₄ -C₂₂ alkyl amido C₂ -C₆alkylene or a mixture thereof, zero or one of said radicals are C₁ -C₆alkyl, zero or one of said radicals is benzyl, or a mixture of a FormulaI and II surfactants; wherein said quaternary ammonium surfactantcomponent has a level of unsaturation in the C₁₄ -C₂₂ alkyl or C₁₄ -C₂₂alkyl amido C₂ -C₆ alkylene radicals, or mixture thereof, sufficient toprovide the unsaturated quaternary ammonium surfactant component with anaverage iodine value of at least 15; and (C) from about 65% to about 99%by weight of the cosmetic composition of a compatible solvent; (b) from0% to about 20%, by weight of the cosmetic composition, of an additionalcosmetic component; and (c) from about 0.05% to about 1.0%, by weight ofthe cosmetic composition, of a mixture of mono-long chain, tri-shortchain quaternary ammonium surfactants of the formula: ##STR20## whereinX is a salt forming anion, a is the ionic charge of X, the quaternaryammonium radical R₁ is C₁₄ -C₂₂ alkyl or C₁₄ -C₂₂ alkyl amido C₂ -C₆alkylene and the quaternary ammonium radicals R₂, R₃ and R₄independently are C₁ -C₆ alkyl or benzyl, wherein zero or one of saidR₂, R₃, and R₄ radicals is benzyl;wherein said cosmetic compositioncomprises no more than about 1.0% of water soluble surfactants, andfurther wherein component (c) is a mixture of (i) C₁₄ -C₂₂ alkyl, C₁ -C₃dialkyl, benzyl ammonium salts, and (ii) unsaturated C₁₄ -C₂₂, tri C₁-C₃ alkyl ammonium salts, and the ratio of (i):(ii) is from about 0.5:1to about 8:1.
 2. The composition of claim 1, wherein said radicals ofFormula I are selected from the group consisting of C₁₄ -C₂₂ alkyl, C₁-C₆ alkyl, benzyl, and C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, and saidradicals of Formula II are selected from the group consisting of C₁₄-C₂₂ alkyl, C₁ -C₆ alkyl, benzyl, and C₁₄ -C₂₂ alkyl amido C₂ -C₆alkylene.
 3. The composition of claim 2, wherein the unsaturatedquaternary ammonium surfactant is selected from the group consisting ofcompounds of Formula I wherein two of said radicals are C₁₆ -C₂₂ alkyl,from one to two of said radicals are C₁ -C₃ alkyl, and zero or one ofsaid radicals is benzyl, and compounds of Formula II wherein two of saidradicals are C₁₆ -C₂₂ alkyl, and one of said radicals is C₁ -C₃ alkyl orbenzyl.
 4. The composition of claim 3, wherein said unsaturatedquaternary ammonium surfactant component is selected from Formula I andcomprises from one to two methyl radicals, zero or one benzyl radical,and two C₁₆ -C₁₈ alkyls.
 5. The composition of claim 1, wherein saidunsaturated quaternary ammonium surfactant comprises a salt of dimethyldi(unsaturated) tallow ammonium, dimethyl di(unsaturated)arachidylammonium, dioleyl dimethylammonium, di-rapeseed alkyl dimethyl ammonium,diricinoleyl dimethyl ammonium, disoyadimonium, olealkonium,methyl-1-oleyl amido ethyl-2-oleyl imidazolinium, dierucyl dimethylammonium, or methyl-1-soya amido ethyl-2-soya imidazolinium.
 6. Thecomposition of claim 1 wherein said polymer (A) comprises a nonioniccellulose ether having nonionic substitution selected from the groupconsisting of methyl, hydroxyethyl, and hydroxypropyl, in an amountsufficient to cause the cellulose ether to be water-soluble and beingfurther substituted with a long chain alkyl radical having 10 to 24carbon atoms in an amount between about 0.2 weight percent and theamount which renders said polymer (A) less than 0.2% by weight solublein water.
 7. The composition of claim 6 wherein the vehicle systemprovides a rheology to the cosmetic composition that is characterized bya shear stress of from 0 to about 50 pascal over a shear rate range offrom about 0.04 sec⁻¹ to about 25 sec⁻¹.
 8. The composition of claim 7wherein the long-chain alkyl radical is attached to the cellulose ethervia an ether linkage.
 9. The composition of claim 8 wherein the polymer(A) comprises a water-soluble hydroxypropyl cellulose substituted with along-chain alkyl radical having 10 to 24 carbon atoms in an amountbetween about 0.2 weight percent and the amount which renders thepolymer (A) less than 1% by weight soluble in water.
 10. The compositionof claim 9 wherein the hydroxyethyl cellulose prior to substitution withthe long chain alkyl group has a molecular weight of about 50,000 to700,000.
 11. The composition of claim 10 wherein the water-solublehydroxyethyl cellulose is substituted with a long chain alkyl radicalhaving about 16 carbon atoms in an amount between about 0.40% to about0.95%, by weight; the hydroxyethyl molar substitution is from about 2.3to about 3.7; and the average molecular weight of the unsubstitutedcellulose is from about 300,000 to about 700,000.
 12. The composition ofclaim 3 which comprises from about 0.05% to about 3.0%. of saidunsaturated quaternary ammonium surfactant component.
 13. Thecomposition of claim 6, wherein said radicals of Formula I are selectedfrom the group consisting of C₁₄ -C₂₂ alkyls, C₁ -C₆ alkyls, benzyl, andC₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, and said radicals of Formula IIare selected from the group consisting of C₁₄ -C₂₂ alkyls, C₁ -C₆alkyls, benzyl, and C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene.
 14. Thecomposition of claim 13, wherein the unsaturated quaternary ammoniumsurfactant is selected from the group consisting of compounds of FormulaI wherein two of said radicals are C₁₆ -C₂₂ alkyls, from one to two ofsaid radicals are C₁ -C₃ alkyls, and zero or one of said radicals isbenzyl and compounds of Formula II wherein two of said radicals are C₁₆-C₂₂ alkyls, and one of said radicals is C₁ -C₃ alkyl or benzyl.
 15. Thecomposition of claim 14, wherein said surfactants of Formula I comprisesfrom one to two methyl radicals and zero or one benzyl radical.
 16. Thecomposition of claim 1 wherein the composition comprises no more thanabout 1% of fatty alcohol materials.
 17. The cosmetic composition ofclaim 1 which is a hair care composition comprising at least about 0.1%of the additional active cosmetic component and wherein said additionalcosmetic component comprises a hair conditioning component selected fromthe group consisting of a volatile silicone fluid having a viscosity ofless than about 10 centipoise at 25° C.; a non-volatile silicone fluidhaving a viscosity of less than about 100,000 centipoise at 25° C.; asilicone gum having a viscosity greater than about 1,000,000 centipoiseat 25° C.; and mixtures thereof.
 18. The cosmetic composition of claim 1wherein said additional cosmetic component comprises a hair stylingpolymer present in said composition at a level of about 0.1%, by weight.19. A composition according to claim 1 which further comprises as theadditional cosmetic component a hair styling/conditioning agent at alevel of 0.1% to about 10% of said composition.
 20. A hair carecomposition according to claim 17 which further comprises as an activecosmetic component a hair styling/conditioning agent at a level of 0.1%to about 10% of said composition.
 21. The composition of claim 19wherein the hair styling/conditioning agent comprises a copolymercomprising C monomers and components selected from the group consistingof A monomers, B monomers, and mixtures thereof, wherein:A is at leastone free radically polymerizable monomer, the amount by weight of Amonomer, when used, being up to about 98% by weight of the total weightof all monomers in said copolymer; B is at least one monomercopolymerizable with A, the amount by weight of B monomer, when used,being up to about 98% of the total weight of all monomers in saidcopolymer, said B monomer being selected from monomers that are polarrelative to A; and C is a polymeric monomer having a molecular weight offrom about 1,000 to about 50,000 and of the general formulaX(Y)_(n)Si(R)_(3-m) (Z)_(m), wherein X is a vinyl group copolymerizable with theA and B monomers, Y is a divalent linking group, R is a hydrogen, loweralkyl, aryl or alkoxy, Z is a polymeric moiety having a number averagemolecular weight of at least about 500, is pendant from said vinylpolymeric backbone after polymerization, and is of the formula ##STR21##wherein R⁴ is alkyl, alkoxy, alkylamino, aryl or hydroxyl, and r is aninteger of from about 5 to about 700, n is 0 or 1, and m is an integerfrom 1 to 3, wherein C comprises from about 0.01% to about 50% of thecopolymer.
 22. The composition of claim 21 wherein the copolymercomprises from about 5% to about 98% A monomer, from about 0.1% to about50% C monomer, and from 0% to about 98% B monomer.
 23. The compositionof claim 19 wherein the hair styling/conditioning agent comprises alipophilic low polarity free radically polymerizable vinyl monomer (A),a hydrophilic polar monomer (B) which is copolymerizable with monomer(A), and a silicone macromer having a weight average molecular weight offrom about 1,000 to about 50,000 based on polydimethylsiloxane of theformula: ##STR22## wherein m is 1, 2 or 3; p is 0 or 1; R" is alkyl orhydrogen; q is an integer from 2 to 6; X is ##STR23## R¹ is hydrogen or--COOH; R² is hydrogen, methyl or --CH₂ COOH; Z is ##STR24## R⁴ isalkyl, alkoxy, alkylamino, aryl, or hydroxyl; and r is an integer fromabout 5 to about
 700. 24. A hair care composition according to claim 23wherein monomer A is selected from the group consisting of acrylic acidesters of C₁ -C₁₈ alcohols, methacrylic acid esters of C₁ -C₁₈ alcohols,styrene, vinyl acetate, vinyl chloride, vinylidene chloride,acrylonitrile, alpha-methylstyrene, t-butylstyrene, butadiene,cyclohexadiene, ethylene, propylene, vinyl toluene, polystyrenemacromer, and mixtures thereof.
 25. A hair care composition according toclaim 24 wherein monomer B is selected from the group consisting ofacrylic acid, methacrylic acid, N,N-dimethylacrylamide,dimethylaminoethyl methacrylate, quaternized dimethylaminoethylmethacrylate, methacrylonitrile, methacryloamide, maleic anhydride,itaconic acid, acrylamide, hydroxyethyl methacrylate, diallyldimethylammonium chloride, vinyl pyrrolidone, maleimides, vinyl pyridine, vinylimidazole, styrene sulfonate, and mixtures thereof.
 26. A hair carecomposition according to claim 25 wherein monomer A is selected from thegroup consisting of n-butylmethacrylate, isobutylmethacrylate,2-ethylhexyl methacrylate, t-butylacrylate, t-butylmethacrylate,methylmethacrylate, and mixtures thereof.
 27. A hair care composition asin claim 1, wherein the weight ratio of the total of the surfactants ofFormula I and Formula II to Formula III is from about 1:1 to about 4:1.28. The composition of claim 27, wherein said radicals of Formula I areselected from the group consisting of C₁₄ -C₂₂ alkyls, C₁ -C₆ alkyls,benzyl, and C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene, and said radicals ofFormula II are selected from the group consisting of C₁₄ -C₂₂ alkyls, C₁-C₆ alkyls, benzyl, and C₁₄ -C₂₂ alkyl amido C₂ -C₆ alkylene.
 29. Thecomposition of claim 28, wherein the unsaturated quaternary ammoniumsurfactant is selected from the group consisting of compounds of FormulaI wherein two of said radicals are C₁₆ -C₂₂ alkyls, from one to two ofsaid radicals are C₁ -C₃ alkyls, and zero or one of said radicals isbenzyl, and compounds of Formula II wherein two of said radicals are C₁₆-C₂₂ alkyls, and one of said radicals is C₁ -C₃ alkyl or benzyl.
 30. Thecomposition of claim 29, wherein said unsaturated quaternary ammoniumsurfactant component is selected from Formula I and comprises from oneto two methyl radicals, zero or one benzyl radical, and two C₁₆ -C₁₈alkyls.
 31. The composition of claim 1, wherein component (c)(i) is oneor more C₁₆ -C₁₈ alkyl dimethyl benzyl ammonium salts, component (c)(ii)is one or more unsaturated C₁₆ -C₁₈ alkyl trimethyl ammonium salts, andthe weight ratio of (c)(i):(c)(ii) is from about 1:1 to about 5:1. 32.The composition of claim 31, wherein the components (c)(i) and (c)(ii)are chloride salts and the weight ratio of (c)(i):(c)(ii) is from about1.5:1 to about 4:1.